Compositions for imparting desired properties to materials

ABSTRACT

The present invention relates to aqueous compositions comprising component (A) which comprises at least one water-soluble component comprising at least one functional group that undergoes a crosslinking reaction, preferably upon drying and/or heating; and component (B) which comprises at least one film-forming material. In particular the composition is a coating composition comprises: (A) at least one polyamidoamine-epihalohydrin resin; and (B) at least one material selected from flexibilizing materials, crosslink inhibiters and combinations thereof in an amount sufficient to impart a cuttability value of less than about 15 to a substrate coated with the coating composition. Component (B) is preferably at least one polymer comprising repeating units derived from an alkyl halide having at least one double bond and an alkene, such as ethylene vinyl chloride. Coated substrates such as coated building units, such as ceiling tiles and wall boards, as well as methods of producing such coated substrates are also provided.

CROSS-REFERENCE TO RELATED APPLICATION

[0001] The present application is a continuation-in-part of U.S.application Ser. No. 09/348,346 filed Jul. 8, 1999, the entiredisclosure of which is expressly incorporated by reference herein.

[0002] This application also expressly incorporates by reference hereinthe entire disclosure of U.S. application Ser. No. __/______ [AttorneyDocket No. P18732], entitled “Compositions for Imparting DesiredProperties to Materials”, which is being concurrently filed with thepresent application.

BACKGROUND OF THE INVENTION

[0003] 1. Field of the Invention

[0004] The present invention relates to aqueous compositions forimparting a variety of characteristics to materials. For example,aqueous compositions of the present invention include compositions forcoating/barrier layers, replacements/extenders for latex, and crosslinkers for a variety of substances, as well as in adhesives/binders.Such compositions can impart various desired properties to substratescoated and/or impregnated therewith. Aqueous compositions of theinvention are especially suitable for coating substrates, such asphysiological substrates, porous substrates, cellulose substrates,textiles, and building materials, such as wood, metal, and glass. Theaqueous composition of the present invention can also be used in inks,dye fixatives, adhesives, sealants, cellulosic products, personal careproducts such as cosmetics and hair styling products, resins, paint,coatings, and non-woven structures to provide adhesion, delivery,surface modification, strength and/or texture, and protection from theeffects of liquids, and vapor and gases. A non-woven structure can be asheet, web, or batt of directionally or randomly oriented fibers ofnatural and/or man-made fibers or filaments, bonded by friction, and/orcohesion and/or adhesion, excluding paper and products which are woven,knitted, tufted, stitch bonded, or felted by wet milling or notadditionally needled, or that are bonded to each other by any techniquesknown in the art. An example of a non-woven structure includes anon-woven fabric which is a flat, flexible porous sheet structureproduced by interlocking layers or networks of fibers, filaments orfilm-like filamentary structure.

[0005] In addition, the composition of the present invention is suitablefor use in metal conversion coatings to enhance corrosion resistance ofand paint adhesion to metal surfaces.

[0006] The present invention also includes products comprising suchcompositions as well as methods of producing such products.

[0007] 2. Background of the Invention and Related Art

[0008] Materials, can be treated with a variety of compositions toimpart desired properties thereto.

[0009] Substrates are often coated with a coating composition to impartdesired characteristics to the substrate, including the surface thereof.

[0010] Various substrates have been coated or otherwise treated withcoating compositions to impart desired characteristics to the substrate,including the surface thereof. For example, a wide variety of buildingand finishing materials exists, which are employed in construction ofstatic structures, such as residences and other buildings, andcommercial structures, schools, public facilities, and the like. Manysuch materials are based on non-woven materials. Further, many suchmaterials are coated and/or impregnated with a surface finish coating,either during manufacture, prior to installation, or post-installation,or in a combination of the above situations.

[0011] Such materials, particularly ceiling tiles, have been providedwith prime coats comprising ethylene-vinyl chloride copolymer emulsions.Particularly suitable materials include those available from AirProducts and Chemicals, Inc., of Allentown, Pa., under the trade nameAIRFLEX®. Specific examples of such emulsions are disclosed in U.S. Pat.No. 4,673,702 to IACOVIELLO, and U.S. Pat. No. 4,962,141 to IACOVIELLO,et al., both assigned to Air Products and Chemicals, Inc., Allentown,Pa., both of which are hereby incorporated by reference as though setforth in full herein.

[0012] Paper for certain applications has been customarily strengthenedwith resins to impart strength thereto when the paper is wet. Suchresins are commonly referred to as “wet strength resins.” A frequentlyemployed wet-strength resin for use in papers is that of the broad classof polyamidoamine-epihalohydrin resin polymers for resins. Such resinsinclude those marketed under the trademark KYMENE® by HerculesIncorporated, Delaware. Such resins, and processes for theirmanufacture, are disclosed in, for example, U.S. Pat. Nos. 2,926,116 and2,926,154, both to KEIM; U.S. Patent No. 5,614,597 to BOWER; U.S. Pat.Nos. 5,644,021 and 5,668,246, both to MASLANKA; all assigned to HerculesIncorporated, all of which patents are hereby incorporated by referenceas though set forth in full herein.

[0013] U.S. Pat. No. 4,859,527 discloses cellulosic non-woven productsof enhanced water and/or solvent resistance obtained by pre-treatment ofthe cellulosic fibers. In some embodiments, this patent discloses thatsuitable pre-treatment agents include poly(aminoamide) epichlorohydrinresins. Suitable overcoat binders are disclosed as includingethylene-vinyl chloride-acrylamide polymers. Specific examples of thepre-treatment agents include KYMENE®, and HERCOBOND®, includingHERCOBOND® 5100; overcoat binders include binders such as AIRFLEX®“EVCl” co-polymers (AIRFLEX® 4500).

[0014] There has also been a need for flexible coatings such aspretreatments and precoats on various substrates. Such substrates onwhich a need for a flexible coating exists include substrates subject tobending and flexing. Such substrates also can include those which can becut. Ceiling tiles are exemplary of such substrates.

[0015] Coating compositions comprising poly(aminoamide) epihalohydrinresins such as KYMENE and latices such as AIRFLEX are used to treatceiling tiles as disclosed in co-pending application Ser. No.09/348,346, which is hereby incorporated by reference as though setforth in full herein.

[0016] Nail polish is another example of a coating for substrates.Aqueous-based nail polishes are disclosed in commonly assignedco-pending application Ser. No. 09/348,345, which is hereby incorporatedby reference as though set forth in full herein. Nail polish is mostcommonly a colored liquid that dries, not unlike paint, into a hard,shiny coating. Nail polishes sold as articles of commerce are typicallysolutions and/or dispersions in an organic solvent, such as toluene oracetone.

[0017] Conventional nail polishes generally employ nitrocellulose as thefilm former. Typical formulations are disclosed in “Formulating NailLacquer”, B. Albert, Drug and Cosmetic Industry, Vol. 48, (November1998), which is hereby incorporated by reference as though set forth infull herein, for its background information on such nail formulations.

[0018] U.S. Pat. No. 5,120,259 discloses a water-based nail polishconsisting of at least one polyurethane and/or polyurethane copolymer indispersed form as a binder, with a thickener and acrylated-styrenecopolymer. The acrylated-styrene copolymer is employed to increasehardness of the dried coating.

[0019] U.S. Pat. No. 5,716,603 discloses a nail polish compositioncomprising an aqueous solution containing an acrylic resin cross linkedwith a difunctional acrylated urethane oligomer. This patent notes thatnail polish formulations contain other additives, such as plasticizersand coalescents to modify the film and/or provide other desired orfunctional properties such as gloss, uniform color or resistance tochipping.

[0020] Changes in the overall formulation of substrate coatings havebeen attempted. For example, attempts have been made to improve physicalproperties such as water resistance, durability, scratch resistance,etc. well as good appearance, including finish color. However, there hasbeen a continuing need for improvement.

[0021] Substrates are often coated with a coating composition to impartdesired characteristics to the substrate, including the surface thereof.Porous building materials are illustrative of such substrates. A widevariety of building and finishing materials exists, which are employedin construction of static structures, such as residences and otherbuildings, and commercial structures, schools, public facilities, andthe like. Many such materials are based on non-woven webs. Further, manysuch materials are coated and/or impregnated with a surface finishcoating, either during manufacture, prior to installation, orpost-installation, or in a combination of the above situations.

[0022] High grade accoustical ceiling tile is marketed for itsappearance and sound characteristics. The manufacture of such materialsmay be generally divided into two stages: a wet end formulation stageand a fabrication stage.

[0023] In the wet end formulation stage, the baseboard tile is made froma slurry mixture of, for example, mineral wool, paper, perlite, clay andstarch, which is drained on a wet-end forming machine or paper machineor similar system and dried, producing a thick mat. In the fabricationstage, the resultant mat is subsequently sanded, cut, designed into apattern and “painted” (or coated). In such products, it is desirable toprovide certain characteristics related to durability, handle abilityand workability. For example, with ceiling tiles, it is extremelyimportant to provide ceiling tiles which exhibit as low flaking andchipping characteristics as possible, particularly when making edge cutsor installing the tiles in the ceiling support grid. Attempts have beenmade to improve these characteristics by modifying the rough stockcomposition of the material fed into the board mill, as well asmodifications to coatings, such as prime coatings, finish paints, finishcoatings and edge coatings. In general, such approaches have includedattempts to modify or provide new raw materials and/or change otherprocesses of manufacture.

[0024] With respect to ceiling tiles, changes in the overall formulationof board material (that is, the slurry from which the board is made) andin the prime coat have been attempted. For example, attempts have beenmade to improve physical properties such as cuttability, durability,scratch resistance, reduction in flaking, chipping, etc., as well asgood appearance, including finish color. However, there has been acontinuing need for improvement.

SUMMARY OF THE INVENTION

[0025] The present invention relates to aqueous compositions comprisingcomponent (A) which comprises at least one water-soluble componentcomprising molecules which interact with or entangle with each other,such as at least one functional group that undergoes a crosslinkingreaction, preferably upon drying and/or heating; and component (B) whichcomprises at least one film-forming material, preferably a latexmaterial.

[0026] The aqueous compositions of the present invention can be used ascoating/barrier layers, replacements/extenders for latex, and crosslinkers, as well as in adhesives/binders. When used as coating/barrierlayers, the aqueous composition of the present invention providesmoisture barrier, edge seal, extenders for latices, stain resistance,water resistance/repellency, and porosity control for porous substrates,such as paper and textiles. Examples of coating/barrier layers include,but are not limited to, additives for texture in paint, binders forcoatings (e.g., in paint), paint primers for all surfaces, additives forpaper (e.g., paper coatings, paper printability, paper sizing, and paperwet/dry strength agent), precoats for coated paper, primers forprinting, and replacements/extenders for latex in all applications usinglatex. In addition, the composition of the present invention is suitablefor use in metal conversion coating to enhance corrosion resistance ofand paint adhesion to metal surfaces.

[0027] The aqueous composition of the present invention can also be usedin adhesives/binders, such as adhesives, binders (e.g., for coatings andpersonal care products such as cosmetics and hair styling products),additives for engineered wood products, dye fixatives, paper wet/drystrength additives, additives in paint, resins such as permanent pressresins (e.g., for wrinkle resistance), precoats for coated papers,primers for printing for any surfaces (e.g., wood, paper, metal, etc.),protective coatings, surface modifiers for wood/metal/glass, andreplacement/extender for latex as internal binders in all applicationsusing latex. When used in an adhesive/binder, the aqueous composition ofthe present invention can provide dimensional stability control and/orstrength for paper, wood, and textiles, as well as texture in paint.

[0028] In addition, the aqueous composition of the present invention canalso be used as cross linkers in additives for engineered wood products,paper sizing agents, paper wet/dry strength additives, permanent pressresins, replacement for latex as internal binders in all applicationsusing latex, surface modifiers in wood/metal/glass, ink vehicles, andtextile wet processing aids. The use of the aqueous composition of thepresent invention as cross linkers provides sealing properties, stainresistance, textile strength, and water resistance repellency

[0029] For example, component (A) can beneficially be selected from atleast one of acrylamide-based crosslinkable polymers (e.g., cationicfunctionalized polyacrylamides.), polyamidoamine-epihalohydrin resins,polyamines, and polyimines.

[0030] In some preferred embodiments, the at least one functional groupof component (A) can be selected from epoxy, azetidinium, aldehyde,carboxyl group, acrylate and derivatives thereof, acrylamide andderivatives thereof, and quaternary amine.

[0031] The film-forming polymer can be selected, for example, from atleast one polymer derived from monomers of alkyl halides of from 2-12 Catoms, alkene halides of from 2-12 C atoms, alkyl acrylamides of from2-12 C atoms, alkene acrylamides of from 2-12 C atoms, alkyl acrylatesof from 2-12 C atoms, and alkene acrylates of from 2-12 C atoms. Somepreferred polymers include those derived from at least one monomerselected from styrene, dimethylstyrene, vinyltoluene, chloroprene,butadiene, ethylene, acrylamide, acrylonitrile, acrolein,methylacrylate, ethylacrylate, acrylic acid, methacrylic acid, methylmethacrylate, n-butyl acrylate, vinylidene chloride, vinyl ester, vinylchloride, vinyl acetate, acrylated urethane, hydroxyethyl acrylate,dimethylaminoethyleneacrylate, and vinyl acetate. For example, thefilm-forming polymer can be a latex selected from at least one polymerderived from at least one monomer comprising repeating units derivedfrom an alkyl halide having at least one double bond, such as a vinylhalide, e.g., vinyl chloride, and an alkene, such as ethylene, whereinthe alkyl halide has from 2 to 12 C atoms, and wherein the alkene hasfrom 2 to 12 C atoms. The alkyl halide can be a vinyl halide, forexample. In some embodiments, the composition further includes at leastone acid, preferably fluoacid (e.g., fluotitanic acid, fluozirconicacid, fluosilicic acid, and fluoboric acid).

[0032] In some preferred embodiments, the composition can have a dryweight ratio of (A) to (B) of about 5:1 to 1:1, more preferably about2:1 to 1:1 or about 1.69:1.

[0033] The invention also relates to methods of preparing a coatedsubstrate comprising, for example coating a substrate with a coatingcomposition including components (A) and (B); and curing the coatingcomposition on the substrate. Further, the methods can include coating asubstrate with a coating composition including components (A) and (B),and drying the composition in place on the surface of a substrate orrinsing a substrate with a coating composition.

[0034] In addition, the present invention is also directed to coatedsubstrate materials coating substrates such as cellulosic products andcoating, non-woven products such as sheets, ceiling tiles, and metal.Preferably, the present invention is also directed to methods ofpreparing coated substrates such as cellulosic products, non-wovensheets, ceiling tiles, and metal using components (A) and (B), e.g., acured composition of components (A) and (B).

[0035] The present invention is also specifically directed to methodsfor metal conversion coating using the composition containing components(A) and (B) and at least one acid, preferably fluoacid (e.g.,fluotitanic acid, fluozirconic acid, fluosilicic acid, and fluoboricacid), preferably at a pH from about 1.5 to about 5.0. Preferably thepresent invention is directed to a method of forming a substantiallychromium-free conversion coating on a metal surface using thecomposition containing components (A) and (B) and at least one acid,preferably fluoacid (e.g., fluotitanic acid, fluozirconic acid,fluosilicic acid, and fluoboric acid), preferably at a pH from about 1.5to about 5.0. More preferably, the present invention is directed to amethod of forming a substantially chromium-free, dried in placeconversion coating on a metal surface using the composition containingcomponents (A) and (B) and at least one acid, preferably fluoacid (e.g.,fluotitanic acid, fluozirconic acid, fluosilicic acid, and fluoboricacid), preferably at a pH from about 1.5 to about 5.0. The amount of thecomposition in (1) can preferably be from about 0.1 to about 90% byweight, and the amount of acid can preferably be from about 0.2 to about20% by weight.

[0036] The present invention is also directed to substrates, preferablymetal substrates comprising a cured composition which comprisescomponent (A) which comprises at least one water-soluble componentcomprising at least one functional group that undergoes a crosslinkingreaction, preferably upon drying and/or heating; and component (B) whichcomprises at least one film-forming material, preferably a latexmaterial

[0037] Further, the present invention also relates to methods ofpreparing cellulosic products, preferably ceiling tiles and non-wovenproducts such as sheets.

[0038] For example, the invention provides a method of substantiallysimultaneously or sequentially adding to a system comprising cellulosicfibers, wherein the system is selected from at least one of aqueoussystem, felt, web, and combinations thereof (A) at least onewater-soluble component comprising at least one functional group thatundergoes a crosslinking reaction; and (B) at least one film-formingpolymer.

[0039] The present invention also relates to cellulosic products,preferably ceiling tiles and non-woven products such as sheetscomprising a composition which comprises component (A) which comprisesat least one water-soluble component comprising at least one functionalgroup that undergoes a crosslinking reaction, preferably upon dryingand/or heating; and component (B) which comprises at least onefilm-forming material, preferably a latex material.

[0040] In some aspects, the present invention provides a coatingcomposition for substrates, and, in particular, porous substrates,especially porous substrates which can be handled or manipulated aftercoating.

[0041] In some aspects, the invention relates to building materials,including ceiling tiles and the like, which exhibit improved cuttabilityas shown by low levels of flaking and/or chipping.

[0042] The present invention provides a coating composition for buildingmaterials, including ceiling tiles and the like, which achieve a desiredfinish color and face durability (such as scratch resistance, abrasionresistance and scrubbability properties).

[0043] Preferably, the invention provides such materials which exhibit acombination of improved cuttability as shown by low levels of flakingand/or chipping and abrasion resistance.

[0044] Also preferably, the invention provides coating compositions forbuilding materials including ceiling tiles, which, when the buildingmaterials are coated with the composition and the composition is cured,exhibit a combination of the foregoing attributes, while also providinggood acoustics, low sag, good durability, good aging characteristics,good color or cover characteristics, good fire resistance, and favorableproperties for installation.

[0045] The coatings of the invention can be applied to a porous typefiber substrate (such as a ceiling tile) and impart durabilityproperties to that substrate without sealing it off, losing porousproperties (such as acoustics) or diminishing aesthetic appearance,while still maintaining a Class A fire performance.

[0046] The invention provides the foregoing advantages. The inventionalso provides a composition that can be easily used.

[0047] The components of the composition can be easily mixed, especiallyin embodiments where they are in liquid form, such as in the form of anemulsions.

[0048] Compositions of the invention when curing do not require a highdegree of ventilation.

[0049] Compositions of the invention are also stable over time.

[0050] Compositions of the invention possess properties which renderthem especially suitable for application to substrates by spraying. Forexample, the compositions of the invention have low viscosities andcontain a low level of solids. Thus, the compositions of the inventionmay be sprayed without substantial plugging of the spraying equipmentduring operation. Additionally, the compositions of the invention may besprayed without the need for large amounts of air for spraying; as aresult of the low viscosity of the compositions, the compositions mayreadily be atomized at lower pump pressures.

[0051] In some aspects, the invention provides a coating compositioncomprising:

[0052] (A) at least one polyamidoamine-epihalohydrin resin; and

[0053] (B) at least one material in an amount sufficient to impart acuttability value of less than about 15 to a substrate coated with thecured coating composition.

[0054] In some aspects, the invention provides a coating compositioncomprising:

[0055] (A) at least one polyamidoamine-epihalohydrin resin; and

[0056] (B) at least one material selected from flexibilizing materials,crosslink inhibitors and combinations thereof in an amount sufficient toimpart a cuttability value of less than about to a substrate coated withthe coating composition.

[0057] In some aspects, the invention provides a coating compositioncomprising:

[0058] (A) at least one polyamidoamine-epihalohydrin resin; and

[0059] (B) at least one polymer comprising repeating units derived froman alkyl halide having at least one double bond an alkene.

[0060] In some aspects, the invention provides building units coatedwith a composition comprising:

[0061] (A) at least one polyamidoamine-epihalohydrin resin; and

[0062] (B) at least one polymer comprising repeating units derived froman alkyl halide having at least one double bond and an alkene.

[0063] In some aspects, the invention provides coating compositionscomprising:

[0064] (A) at least one polyamidoamine-epihalohydrin resin; and

[0065] (B) at least one material in an amount sufficient to impartsufficient flexibility, such that when the coating is applied to asubstrate and cured, the cured coating exhibits substantially nodelamination from the substrate or cracking, when the substrate is bentsubstantially 180° subsequent to curing. The thickness of the coatingafter curing is preferably in the range of about 5-10 mils when cured.

[0066] Preferably, such compositions exhibit sufficient flexibility,such that when the coating is applied to a substrate and cured, thecured coating exhibits substantially no delamination or cracking, whenthe substrate is bent substantially 360°.

[0067] Component (A) can comprise an aqueous solution of component (A)present in an amount in a range of from about 5% to about 95% by weightbased on the total weight of all components of the composition, andcomponent (B) can comprise an aqueous emulsion of component (B) presentin an amount in a range of from about 5% to about 95% by weight based onthe total weight of all components of the composition. Component (A) cancomprise an aqueous solution of component (A) present in an amount in arange of from about 50% to about 85% by weight based on the total weightof all components of the composition, and component (B) can comprise anaqueous emulsion of component (B) present in an amount in a range offrom about 8% to about 50% by weight based on the total weight of allcomponents of the composition. Component (A) can comprise an aqueoussolution of component (A) present in an amount of about 75% by weightbased on the total weight of all components of the composition, andcomponent (B) can comprise an aqueous emulsion of component (B) presentin an amount of about 11% by weight based on the total weight of allcomponents of the composition.

[0068] The coating compositions can further comprise a surfactant. Thesurfactant can comprise an octylphenoxypolyethoxyethanol nonionicsurfactant. The surfactant can be present in an amount of up to 5%, byweight. The surfactant may be present in an amount of up to about 1% byweight. The surfactant may be present in an amount of about 0.05-0.25%by weight.

[0069] In such compositions, the weight ratio of (A):(B) is from about0.05 to about 19, preferably about 4 to about 12, more preferably fromabout 6 to about 8, more preferably about 6.5 to about 7.0, and morepreferably about 6.75.

[0070] The invention also provides coated building units comprising asubstrate such coating compositions as set forth above. The substratecan comprise a ceiling tile or a wall board.

[0071] Such coated building units exhibit a Hess Rake Test Value of atleast about 8, and a cuttability value of less than about 15.

[0072] Preferably such coated building units exhibit a Hess Rake TestValue at least about 10, and a cuttability value of less than about 10;preferably a Hess Rake Test Value of at least about 12, and acuttability value of less than about 2; preferably a Hess Rake TestValue of at least about 14, and a cuttability value of less than about1.

[0073] The substrate can comprise a ceiling tile and/or a wall board.

[0074] Preferably such coated building units exhibit a Hess Rake TestValue range of at least about 8, and a cuttability value of less thanabout 15; preferably a Hess Rake Test Value of at least about 10, and acuttability value of less than about 10; more preferably a Hess RakeTest Value of at least about 12, and a cuttability value of less thanabout 2; and more preferably a Hess Rake Test Value of at least about14, and a cuttability value of less than about 1.

[0075] Component (B) is preferably selected from copolymers which may bederived from monomers including at least one of alkyl halides, alkenes,methyl methacrylate, butyl acrylate, styrene vinylidene chloride,acrylic acid, methacrylic acid, and vinyl acrylic-based materials.

[0076] Component (B) preferably comprises an alkyl halide, preferably avinyl halide, and preferably vinyl chloride. Preferably the alkenecomprises an olefin, preferably ethylene.

[0077] The invention also provides methods of producing a coatedsubstrate comprising

[0078] (1) coating a substrate with a coating composition comprising:

[0079] (A) at least one polyamidoamine-epihalohydrin resin; and

[0080] (B) at least one material in an amount sufficient to impart acuttability value of less than about 15 to the coated substrate uponcuring the coating composition; and

[0081] (2) curing the coating composition on the substrate. Preferably,the cuttability value is less than about 10, more preferably less thanabout 2, more preferably less than about 1. The substrates andcompositions employed can be as defined above.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0082] The present invention relates to aqueous compositions comprisingcomponent (A) as defined herein and component (B) as defined herein.

[0083] The aqueous compositions of this invention have various utilitiesincluding uses as coating/barrier layers, replacements/extenders forlatex, and cross linkers, as well as uses in adhesives/binders. Whenused as coating/barrier layers, the aqueous composition of the presentinvention provides moisture barrier, edge seal, extenders for latices,stain resistance, water resistance/repellency, and porosity control forporous substrates. Examples of porous substrates include, but are notlimited to, paper products, non-woven products such as sheets, andtextiles. “Extender of latices” refers to the ability of the compositionof the present invention (i.e., components (A), and (B)) to be asubstitute for latex, and can be used in place of or partialsubstitution for a latex in any applications where latex could be used.

[0084] Examples of coating/barrier layers include, but are not limitedto, additives for texture in paint, binders for coatings (e.g., inpaint), paint primers for all surfaces, additives for paper (e.g., papercoatings, paper printability, paper sizing, and paper wet/dry strengthagent), precoats for coated paper, primers for printing, andreplacements/extenders for latex as internal binders in all applicationsusing latex.

[0085] The aqueous composition of the present invention can be used inadhesives/binders, such as adhesives, binders (e.g., for coatings andpersonal care products such as cosmetics and hair styling products),additives for engineered wood products, dye fixatives, paper wet/drystrength additives for cellulosic products (e.g., non-woven productssuch as sheets and ceiling tiles), additives in paint, resins such aspermanent press resins (e.g., wrinkle resistance), precoats for coatedpapers, primers for printing, protective coatings, surface modifiers forwood/metal/glass, and replacement/extender for latex as internal bindersin all applications using latex. When used in an adhesive/binder, theaqueous composition of the present invention can provide dimensionalstability control and/or strength for paper, wood, and textiles, as wellas texture in paint (such that when a paint is dry, it forms a surfacehaving irregular contours).

[0086] The aqueous composition of the present invention can also be usedas cross linkers in additives for engineered wood products, paper sizingagents, paper wet/dry strength additives, permanent press resins,replacement for latex as internal binders in all applications usinglatex, surface modifiers in wood/metal/glass, ink vehicles (whichprovide impact to ink set and gloss), and textile wet processing aids.The use of the aqueous composition of the present invention as crosslinkers provides sealing properties, stain resistance, textile strength,and water resistance repellency.

[0087] In addition, the present invention is also directed to methods ofpreparing coated substrates such as cellulosic products, non-wovenproducts such as sheets, ceiling tiles, and metal. Preferably, thepresent invention is also directed to methods of preparing coatedsubstrates such as cellulosic products, non-woven sheets, ceiling tiles,and metal using components (A) and (B).

[0088] The invention also relates to methods of preparing a coatedsubstrate comprising, for example coating a substrate with a coatingcomposition including components (A) and (B); and curing the coatingcomposition on the substrate. Further, the present invention includesmethods for metal conversion coating which includes coating a substratewith a coating composition including components (A) and (B), and dryingthe composition in place on the surface of a substrate or rinsing asubstrate with a coating composition. The methods of metal conversioncoating comprise using the composition containing components (A) and (B)and at least one acid, preferably fluoacid (e.g., fluotitanic acid,fluozirconic acid, fluosilicic acid, and fluoboric acid), preferably ata pH from about 1.5 to about 5.0. Preferably the present invention isdirected to a method of forming a substantially chromium-free conversioncoating on a metal surface using the composition containing components(A) and (B) and at least one acid, preferably fluoacid (e.g.,fluotitanic acid, fluozirconic acid, fluosilicic acid, and fluoboricacid), preferably at a pH from about 1.5 to about 5.0. More preferably,the present invention is directed to a method of forming a substantiallychromium-free, dried in place conversion coating on a metal surfaceusing the composition containing components (A) and (B) and at least oneacid, preferably fluoacid (e.g., fluotitanic acid, fluozirconic acid,fluosilicic acid, and fluoboric acid), preferably at a pH from about 1.5to about 5.0.

[0089] “Substantially chromium-free conversion coating” refers to aconversion coating that does not intentionally include added chromium,but can contain a trace amount of chromium.

[0090] Further, the present invention also relates to methods ofpreparing cellulosic products, preferably ceiling tiles and non-wovenproducts such as sheets using the composition containing components (A),and (B). Specifically the present invention relates to methods ofpreparing cellulosic products which comprise (1) substantiallysimultaneously or sequentially adding a composition to a systemcomprising cellulosic fibers, wherein the system is selected from atleast one of aqueous system, felt, web, and combinations thereof, andwherein the composition comprises (A) at least one water-solublecomponent comprising at least one functional group that undergoes acrosslinking reaction; and (B) at least one film-forming polymer.

[0091] “Substantially simultaneously adding” or “simultaneously adding”refers to adding two substances to a slurry or suspension (e.g., such asa cellulosic slurry) with substantially no time difference andessentially at the same position in the system or process. The twosubstances being added can be in the form of a mixture as well asseparately added, e.g., by adding one substance during the addition ofthe other.

[0092] “Sequential addition” refers to at least two different substancesbeing added to different locations at the same time or at a differenttime and/or the same location at different time on a machine used toprepare cellulose products. These locations are far away enough so thatthe one substance added is mixed with the cellulose slurry beforeanother substance is added. A combination of sequential and simultaneousaddition may also be employed.

[0093] In some aspects, the present invention relates to the discoverythat compositions comprising mixtures comprising: component (A)comprising a polyamidoamine-epihalohydrin, and component (B) comprisinga component which cooperates with or moderates the properties ofcomponent (A) and preferably selected from flexiblizing components,components which inhibit cross-linking, and mixtures thereof, provide anunexpectedly superior spectrum of properties when applied as a coatingto various substrates. Compositions of the invention are especiallysuitable for coating porous substrates. Exemplary substrates includebuilding materials, such as ceiling tiles, wall boards and the like. Inaccordance with one definition as used herein, without wishing to bebound by theory, it is believed that the flexibilizing componentfunctions, at least in part, to hinder cross-linking of component (A).

[0094] Component (A)

[0095] Component (A) may be any component having molecules which undergomolecular interaction such as molecular entanglement, crosslinking,molecular bonding, etc. upon drying and/or heating. Without wishing tobe bound by theory, suitable materials for component (A) include, butare not limited to, materials that interact on a molecular level to forma network distributed within component (B) when components (A) and (B)are cured.

[0096] As discussed above, component (A) of the aqueous composition ofthe present invention can comprise at least one water-soluble componentcomprising at least one functional group that undergoes a crosslinkingreaction, preferably upon drying and/or heating. “Water-solublecomponent” refers to a component that dissolves in water to form ahomogeneous liquid. Examples of suitable functional groups of component(A) preferably include, but are not limited to, epoxy, azetidinium,aldehyde, carboxyl group, acrylate and derivatives thereof, acrylamidebase and derivatives thereof, and quaternary amine, more preferablyazetidinium, epoxy, and aldehyde, and most preferably azetidinium andepoxy.

[0097] Examples of component (A) preferably include, but are not limitedto, acrylamide-based crosslinkable polymers,polyamidoamine-epihalohydrin resins, and polyamines, and polyimines,more preferably cationic functionalized polyacrylamides (HERCOBOND 1000®manufactured by Hercules Incorporated) such as those disclosed in U.S.Pat. No. 5,543,446 which is incorporated herein by its entirety, crepingaids such as CREPETROL® A 3025 disclosed in U.S. Pat. No. 5,338,807which is incorporated herein by its entirety, andpolyamidoamine-epihalohydrin resins such as those disclosed in U.S. Pat.Nos. 2,926,116 and 2,926,154, to KEIM, incorporated by reference intheir entirety herein.

[0098] In some aspects of the present invention, the preferred materialsfor component (A) include polyamidoamine-epihalohydrin resins such asthose disclosed in U.S. Pat. Nos. 2,926,116 and 2,926,154, to KEIM,incorporated by reference in their entirety herein. Preferredpolyamidoamine-epihalohydrin resins can also be prepared in accordancewith the teachings of U.S. Pat. No. 5,614,597 to BOWER and commonlyassigned to Hercules Incorporated, incorporated by reference in theirentirety herein. As discussed in U.S. Pat. No. 5,614,597 to BOWER, theseprocesses typically involve reacting aqueous polyamidoamine with anexcess of epihalohydrin to completely convert amine groups in thepolyamidoamine to epihalohydrin adducts. During the reaction halohydringroups are added at the secondary amine groups of the polyamidoamine asshown in the following example, using epichlorohydrin as theepihalohydrin:

[0099] where R₂N— represents a secondary amine group of thepolyamidoamine.

[0100] After the epihalohydrin has been added and when heat evolutionhas subsided, the reaction mixture is heated to effect crosslinking andviscosity increase. During this reaction, azetidinium groups are formed.These functional groups are typically employed to impart wet strength topaper by forming a strong crosslinked network with the paper fibers.

[0101] Preferred polyamidoamine-epihalohydrin resins includepolyamidoamine-epichlorohydrins such as those sold by HerculesIncorporated of Wilmington, Del., under various trade names. Preferredpolyamidoamine-epihalohydrin resins available from Hercules include theKYMENE® resins and the HERCOBOND® resins. KYMENE 557H® resin; KYMENE557LX® resin; KYMENE 557SLX® resin; KYMENE 557ULX® resin; KYMENE 557ULX®resin; KYMENE 709® resin; KYMENE 736® resin; and HERCOBOND 5100® resin.Of these, KYMENE 557H® resin and HERCOBOND 5100® are especiallypreferred polyamidoamines, available in the form of aqueous solutions.KYMENE 763® resin (a polyamine) can also be employed as component (A).It is expressly contemplated that equivalents to each of the foregoingresins are within the scope of the present invention.

[0102] Component (B)

[0103] Without wishing to be bound by theory, suitable materials forcomponent (B) include any materials that are capable of forming acontinuous phase that can be modified by the network structure ofcomponent (A) described above. As discussed above, component (B)comprises at least one film-forming material such as a polymer,preferably a latex material.

[0104] Examples of other film-forming material of the present inventionpreferably include, but are not limited to, polymers derived frommonomers including at least one of alkyl halides of from 2-12 C atoms,alkene halides of from 2-12 C atoms, alkyl acrylamides of from 2-12 Catoms, alkene acrylamides of from 2-12 C atoms, alkyl acrylates of from2-12 C atoms, and alkene acrylates of from 2-12 C atoms.

[0105] In some aspects of the present invention, the film-forming layeris a latex selected from at least one polymer comprising repeating unitsderived from an alkyl halide having at least one double bond and analkene, wherein the alkyl halide has from 2 to 12 C atoms, and whereinthe alkene has from 2 to 12 C atoms.

[0106] “Latex” refers to an aqueous dispersion of a water-insolublepolymer. Latex materials are prepared in an emulsion polymerizationprocess wherein the insoluble monomer is emulsified, with a surfactant,into small particles of less than about 10,000 nm or 10 microns indiameter in water and polymerized using a water-soluble initiator. Theresultant product is a colloidal suspension of fine particles,preferably about 50 to 1000 nm in diameter. See, for example,Kirk-Othmer Encyclopedia of Chemical Technology, fourth edition, volume15, page 51 (J. Wiley & Sons, New York, 1995), which is herebyincorporated herein in its entirety. “Colloidal suspension” refers to adispersion of fine droplets or particles in a liquid medium.

[0107] Suitable latices can be readily identified by those of ordinaryskill in the art, based on physical properties using fully conventionalconsiderations, including stability, rheology, film formation and filmproperties, interfacial reactivity and substrate adhesive can bedetermined by colloidal and polymeric properties of the latex. Colloidalproperties include particle size and morphology distribution solids, pH,viscosity, and stability. Molecular weight distribution, monomersequence and distribution, glass-transition temperature andcrystallinity are well known in the art.

[0108] Latex applications include, but are not limited to, uses asadhesives, binders, coatings, elastic materials, foam products,modifiers, and supports for immobilization of other materials.

[0109] Commercially available latices are derived from a large varietyof monomers including, but not limited to, styrene, dimethylstyrene,vinyltoluene, chloroprene, butadiene, ethylene, acrylamide,acrylonitrile, acrolein, methylacrylate, ethylacrylate, acrylic acid,methacrylic acid, methyl methacrylate, n-butyl acrylate, vinylidenechloride, vinyl ester, vinyl chloride, vinyl acetate, acrylatedurethane, hydroxyethyl acrylate, dimethylaminoethyleneacrylate, andvinyl acetate.

[0110] Other examples of the latex material preferably include, but arenot limited to, copolymers of alkyl halides and alkene halides, such ascopolymers of vinyl or allyl halides and alkenes. Any akyl halides andany alkene halides, which copolymerize to form copolymers with eachother, may be employed. Standard textbooks list exemplary materials.See, for example, Organic Chemistry, Morrison & Boyd, Allyn and Bacon,Inc. 1973, which is hereby incorporated by reference as though set forthin full herein for its disclosure of such materials. Preferred alkylhalides include allyl and/or vinyl halides of from 2-12 C atoms,preferably from 2-6 C atoms, more preferably from 2-4 C atoms and mostpreferably about 2 C atoms. Copolymers of vinyl halides (especiallyvinyl chloride) and alkenes, preferably of from 2-12 C atoms, preferablyfrom 2-6 C atoms, more preferably from 2-4 C atoms and most preferablyof about 2-3 C atoms, especially propylene and/or ethylene, areespecially preferred.

[0111] In some aspects of the present invention, component (B) cancomprise any component that functions to cooperate with or moderate theproperties of component (A). In accordance with one definition herein,materials for component (B) comprise materials that function toflexibilize component (A) after the compositions of the invention areapplied as a coating, materials that tend to inhibit crosslinking ofcomponent (A), and mixtures of such materials are considered exemplary.Materials for component (B) are not limited to these exemplarydefinitions, however.

[0112] The degree to which component (A) is flexibilized by component(B) may be expressed in terms of a cuttability value. An exemplaryprocedure for determining the cuttability value of a substrate (such asa ceiling tile or a wall board) coated with the composition of theinvention is set forth in the Examples, below. The degree to whichcomponent (A) is flexibilized by component (B) may be expressed in termsof the degree to which a substrate (such as a sheet of aluminum, such asa pie pan), coated with a composition of the invention which issubsequently cured, can be bent substantially without cracking ordelaminating the coating from the substrate. An exemplary procedure fordetermining this degree of flexibility is also set forth in theExamples, below.

[0113] Preferred materials for component (B) include copolymers of alkylhalides and alkenes, such as copolymers of vinyl or allyl halides andalkenes. Any akyl halide and any alkene, which copolymerize to formcopolymers with each other, may be employed. Standard textbooks listexemplary materials. See, for example, Organic Chemistry, Morrison &Boyd, Allyn and Bacon, Inc. 1973, which is hereby incorporated byreference as though set forth in full herein for its disclosure of suchmaterials. Preferred alkyl halides include allyl and/or vinyl halides offrom 2-12 C atoms, preferably from 2-6 C atoms, more preferably from 2-4C atoms and most preferably about 2 C atoms. Copolymers of vinyl halides(especially vinyl chloride) and alkenes, preferably of from 2-12 Catoms, preferably from 2-6 C atoms, more preferably from 2-4 C atoms andmost preferably of about 2-3 C atoms, especially propylene and/orethylene, are especially preferred.

[0114] Any copolymers of vinyl chloride and ethylene may be employed ascomponent (B). Exemplary copolymers of vinyl chloride and ethylene aredisclosed in U.S. Pat. No. 4,673,702 to IACOVIELLO, and U.S. Pat. No.4,962,141 to IACOVIELLO, et al., incorporated by reference in theirentireties herein. These copolymers (also referred to herein as “EVCl”copolymers) may be prepared in any way. By way of example, they may beprepared (preferably in the form of an emulsion) as described in U.S.Pat. No. 4,962,141 to IACOVIELLO et al. by the following procedures.

[0115] Suitable EVCl copolymer emulsions may be prepared bycopolymerizing the monomers in the presence of suitable emulsifyingagents, i.e., protective colloids and surfactants, in an aqueous mediumunder pressures generally not exceeding about 100 atm and in thepresence of a redox system which is added incrementally. Thecopolymerization reaction is performed under an ethylene pressure whichis sufficient to provide the copolymer with about 5 to 35 wt % ethylenecontent, preferably about 15 to 25 wt %. Pressures of about 50 to 100atm are generally used to afford such an ethylene content.

[0116] The EVCl copolymer emulsions may additionally contain from 0.1 to30 wt % of an external crosslinking agent based upon the total weight ofthe copolymer. Suitable external crosslinking agents includemelamine/formaldehyde resins, polyisocyanates such as water dispersiblepolymeric methyl diphenyl diisocyanates and water based phenolic resins.

[0117] In carrying out the polymerization, substantially all of thepolyvinyl alcohol and a portion of the vinyl chloride is initiallycharged into the polymerization vessel which is then pressurized withethylene. Most advantageously, at least about 5 wt % and preferably, atleast about 15 wt % of the total vinyl chloride to be polymerized isinitially charged into the reactor. The remainder of the vinyl chlorideis added, desirably at a substantially uniform rate, after the initiallycharged vinyl chloride monomer content has been substantially reduced asevidenced by a decrease in the rate of polymerization. This controlledaddition avoids over pressurization of the reactor. No more than about60% of the vinyl chloride should be charged initially since a prepolymercan be generated in-situ in order to obtain the desired stableemulsions.

[0118] The quantity of ethylene entering the copolymer is influenced bythe pressure, the mixing, the addition rate and amount of free radicalgenerating source. The ethylene content of the copolymer can beincreased by utilizing a higher ethylene pressure, increasing agitationduring mixing or employing a higher free radical source rate.

[0119] The process of forming the EVCl copolymer emulsions may comprisepreparing an aqueous solution containing substantially all of apolyvinyl alcohol dispersing agent. This aqueous solution and theinitial charge of vinyl chloride may be added to the polymerizationvessel and ethylene pressure may then be applied to the desired value.The mixture is mixed thoroughly to dissolve ethylene in the vinylchloride and into the water phase. The charge can be convenientlyelevated to polymerization temperature during this mixing period. Apolymerization temperature of about 55° C. and an ethylene pressure inthe range of 750 psig to 1000 psig may be employed to provide acopolymer with about 20-30 wt % ethylene. Mixing can be effected bymeans of an agitator or other known mechanism.

[0120] The polymerization is initiated by introducing initial amounts ofa free radical generating source into the reactor vessel containing themonomer premix. When employing a redox system, either the oxidant orreductant component can be added initially to the aqueous mediumcontaining the polyvinyl alcohol and vinyl chloride with the other redoxcomponent added to initiate the reaction. Upon initiating thepolymerization, any desired monomer such as the hydroxyalkyl- orcarboxylic acid-containing functional co-monomers disclosed herein maybe added incrementally to the reaction vessel. sustaining and desirablyuntil the residual vinyl chloride content is below 0.5%. The completedreaction product is removed from the presence of ethylene and maintainedat a temperature above the Tg of the copolymer while sealed from theatmosphere. The reaction mixture can also be transferred to a degasserfor removal of unreacted ethylene.

[0121] It will be readily appreciated by those of ordinary skill in theart that the foregoing is exemplary only, and that the genericallyand/or specifically defined reactants and conditions can be substitutedby equivalent reactants and conditions. Especially preferred copolymersfor component (B) include those marketed by Air Products and Chemicals,Inc., of Allentown, Pa., under the trade name AIRFLEX®; especially,AIRFLEX 4530®, AIRFLEX 4514®, AIRFLEX 4500®. It is expresslycontemplated that equivalents to such vinyl chloride/ethylene copolymersare within the scope of the present invention. Thus, for example, anypolymer or copolymer which moderates component (A) such as byfunctioning to flexibilize component (A), and/or any polymer orcopolymer that inhibits crosslinking such that when the water from thecomposition is driven off, and the coating is cured, can be bent 180°,preferably 360°, without cracking or delaminating, is within the scopeof the invention. Preferably any copolymer which functions toflexibilize component (A), and/or any polymer or copolymer that inhibitscrosslinking such that when the coating is applied to a substrate, suchas an aluminum sheet and the water from the composition is driven off,the coating can be bent 180°, preferably 360°, without cracking ordelaminating from the substrate, is within the scope of the invention.Preferably, the combination of components (A) and (B) result incompositions exhibiting good memory, in addition to the good flexibilitydiscussed above. For example, such compositions preferably exhibit goodmemory such that a cured coating when deformed will return to theposition or configuration in which it was before it was deformed.

[0122] Other materials for component (B) include, but are not limitedto, NEOCAR® manufactured by Union Carbide (vinyl ester/acrylic acid),RES 3077® manufactured by Rohm & Haas (vinyl acetate/acrylic acid),FLEXTHANE 620® by Air Products (vinyl chloride amide terpolymer), VINAC884® by Air Products (vinyl acetate), DOW 620® by Dow Chemical Company(styrene butadiene rubber), FLEXBOND 325® (vinyl acetate-acryliccopolymer latex) by Air Products, LUCIDENE 243® (styrene-acrylic polymeremulsion), HYCAR 26256® (acrylic ester copolymer latex) and MORKOTE1725® (acrylic copolymer emulsion).

[0123] As discussed above, such materials for component (B) includewater compatible systems such as copolymers that can contain thefollowing monomers: methyl methacrylate, butyl acrylate, styrenevinylidene chloride, acrylic acid, and methacrylic acid. Suitablecopolymers include acrylated urethanes prepared by reacting a hydroxyacrylate or methacrylate; a diol, polyester or diamine; and adiisocyanate can be used. Preferred monomers are disclosed in U.S. Pat.No. 5,716,603, which is hereby incorporated by reference as though setforth in full herein for its teachings in this regard. Other copolymersthat appear to be useful include acrylic and vinyl acrylic-basedmaterials.

[0124] Other examples of (B) include, but are not limited to, vinylester/acrylic, vinyl acetate/acrylic, vinyl acetate/ethylene, vinylchloride amide terpolymer, vinyl acetate, and styrene/butadiene.

[0125] Other materials for component (B) can also include FLEXBOND 325®(vinyl acetate-acrylic copolymer latex), LUCIDENE 243® (styrene-acrylicpolymer emulsion), HYCAR 26256® (acrylic ester copolymer latex) andMORKOTE 1725® (acrylic copolymer emulsion).

[0126] Compositions

[0127] The aqueous compositions of the invention are preferably employedin the form of an aqueous admixture, preferably an aqueous emulsion, andconveniently in preferred embodiments, in the form of an aqueousemulsion system resulting from the admixture of component (A) andcomponent (B). In addition, the aqueous composition of the presentinvention can include, water and at least one surfactant and/oradditive.

[0128] The pH of the aqueous composition containing components (A) and(B) can be adjusted to suit particular utilities. Preferably, the pH isfrom about 3 to about 9, more preferably from about 3 to about 7, andmost preferably about 4.5.

[0129] The present invention is preferably prepared by adding 75 g ofcomponent (A), preferably Hercobond 5100® or Kymene 557H® to 11.11 g anemulsion of component (B), preferably Airflex 4530® with mechanicalstirring and adding water to make a 100 g solution.

[0130] The coating compositions of the invention are preferably employedin the form of an aqueous admixture, preferably an aqueous emulsion, andconveniently in preferred embodiments, in the form of an aqueousemulsion system resulting from the admixture of an solution of component(A) and an emulsion of component (B), and optionally water and asurfactant.

[0131] Thus, compositions of the invention may be prepared by mixingcommercially available solutions of component (A) and component (B).Because such products are commercially available, it is expedient andconvenient to employ components (A) and (B) “as received” from thesuppliers, although this is not required. As illustrative examples, suchsolutions are available in concentrations of about 12.5% ((convenientlyexpressed as percent solids) based on weight of resin to total weight of“as received” solution) for component (A), and concentrations of about50% (based on weight of resin to total weight of “as received” emulsion)for component (B).

[0132] At concentrations of about 12.5% for an solution of component (A)and about 50% for an emulsion of component (B), solutions of component(A) are employed in the compositions in amounts of from about 5 to about95%, preferably from about 50% to about 85%, more preferably about 75%(based on the total weight of all components of the composition), andemulsions of component (B) are employed in the compositions in amountsof from about 5% to about 95%, preferably from about 8% to about 50%,more preferably about 11% (based on the total weight of all componentsof the composition). Compositions of about 75% for component (A) and11.11% for component (B) have been found to be particularly preferred,with the remaining components of the composition being surfactant(preferably in an amount of about 0.06%), and water.

[0133] This may also be expressed such that, the compositions of theinvention may have content of solids of component (A) (in terms ofactive ingredient, i.e., resin) in a range of from about 1% to about85%, preferably about 1.5% to about 82.5%, most preferably about 63%(based on the total weight of the two resins, i.e., based on the totalweight of the resins of component (A) and (B)), and content of resin ofcomponent (B) (in terms of active ingredient, ie., resin) in a range offrom about 15% to about 99%, more preferably about 17.4% to about 98.7%,most preferably about 37% (based on the total weight of the two resins,i.e., based on the total weight of the resins of component (A) and (B)).

[0134] The amounts of component (A) and component (B) employed in theaqueous compositions of the invention may also be expressed in terms ofa ratio (A):(B), based on dry weight of polymer of component (A) to thedry weight of the polymer of component (B). The aqueous compositions ofthe invention preferably include those wherein the ratio of (A):(B) isfrom about 5:1 to about 1:5, more preferably from about 2:1 about toabout 1:1, and more preferably from about 1.69:1.

[0135] The amounts of component (A) and component (B) employed in thecompositions of the invention may also be expressed in terms of a ratio(A):(B), based on the weight of polymer of component (A) to the weightof the polymer of component (B) (that is (A)/(B), compositions of theinvention include those wherein the ratio of (A):(B) is from about 0.05to about 19, preferably from about 4 to about 12, more preferably fromabout 6 to about 8, more preferably from about 6.5 to about 7.0, mostpreferably about 6.75.

[0136] Optional Surfactants and Additives

[0137] In preparing the aqueous compositions of the invention, solutionsof components (A) and (B), water, and optionally, at least onesurfactant and/or at least one additive and/or a least one acid, may bemixed in any suitable mixing vessel, preferably with agitation, such asstirring. A mixing vessel equipped with a stirrer may be employedparticularly for this purpose. These components may be added to themixing vessel in any order of addition, or concurrently.

[0138] The compositions also preferably comprise a surfactant. Suitablesurfactants include non-ionic, anionic and cationic surfactants.TERGITOL®, TRITON GR7M®, TRITON X 100®, Triethylamine (TEA), AQUAQUEST2120® (available from GEO Specialty Chemicals, Cedertown, Ga.) and waterare exemplary. A preferred surfactant is TRITON X-100® (anoctylphenoxypolyethoxyethanol nonionic surfactant) available from UnionCarbide Chemicals and Plastics Company, Incorporated, Danbury, Conn.Surfactants are preferably employed in amounts of up to about 10%, byweight. Preferred ranges for amounts of surfactant are in the range ofabout 0-5%, by weight; more preferably about 0-1%, most preferably,surfactants are employed in amounts of about 0.05-0.25% by weight, basedon the total weight of the composition.

[0139] The aqueous composition of the present invention can also includeadditives, such as pigments to provide colors. Suitable pigments includethose of the organic type and those of the inorganic type. Preferredorganic pigments include D and C Red, Nos. 10, 11, 12 and 13, D and CRed No. 7, D and C Red Nos. 5 and 6, D and C Red Nos.30 and 40, D and CYellow No. 5 and D and C Red No. 2. Inorganic pigments include titaniumdioxide, bismuth oxychloride, brown iron oxide and the red iron oxides.

[0140] The pigments may preferably be employed in amounts of up to about5% by weight, preferably from about 0.01% to about 5% by weight, morepreferably in amounts of from about 0.5% to about 2%, by weight.

[0141] Other ingredients may be added to accelerate drying. Theseinclude glycol esters, such as butyl glycol acetate, and volatilealcohols such as ethanol and 2-propanol. Drying accelerators may beadded in amounts of from of up to about 5%, by weight, more preferablyfrom about 0.01% by weight to about 5% by weight; more preferably fromabout 0.5% to about 2.5% by weight.

[0142] Other ingredients such as plasticizers and coalescing agents mayalso be employed. These include, for example, those disclosed in U.S.Pat. No. 5,716,603, which patent is hereby incorporated by reference asthough set forth in full herein.

[0143] Thickeners may also be employed, in amounts in a range of fromabout 0.01% to about 5% by weight, for example. Suitable thickenersinclude cellulose and derivatives, including carboxymethylcellulose andhydroxyethyl cellulose, natural gums such as carrageenan, pectin andxanthan gum, silicates, clays, such as laponite and synthetic polymerssuch as ethylene oxide, vinyl alcohol, acrylic or polyurethane-typepolymers, and the like.

[0144] Common practice has been to add fillers to the coatings to giveproperties of face durability, color and fire performance. However, ahigh amount of fillers (for example, 40% or greater by weight) willtypically form a plate-like sealed surface on the board, which isdesirable for face durability but will hurt the acoustical properties.They also prevent the coating from soaking into the board, and cause thepaint to chip when a cut is made. Fillers also serve to “hide” the colorof the substrate (in many compositions, the binder itself will not hidethe substrate).

[0145] Additives can also be employed. The term “additives” includes abroad range of solid and liquid materials normally added to coatingcompositions. Suitable additives can be readily identified and employedby those of ordinary skill in the art. Additives include fillers, suchas silicas, clays (including Kaolin, Ball, Delaminated, Calcined, etc.);calcium carbonate, titanium dioxide, pigments, optical brighteners, etc.When employed, additives may be employed in amounts in the range of fromabout 0-40%, based on total weight of the composition.

[0146] Suitable acids that can be used in combination with thecomposition of the present invention include, but are not limited to,fluoacid. Examples of fluoacid include, but are not limited to,fluotitanic acid, fluozirconic acid, fluosilicic acid and fluoboricacid, preferably fluotitanic acid and fluozirconic acid.

[0147] Uses of Composition

[0148] As discussed above, the aqueous compositions of the presentinvention can be used as additives for texture in paint, additives forengineered wood products, adhesives, binders for coating, controlporosity of paper and textiles, dimensional stability control for paper,wood and textiles, dye fixative, edge seal, edge seal extenders forlatices, hair styling, ink vehicles, latex replacement/extender,moisture barriers, paint binders, paint primers for all surfaces, papercoating additives, paper printability additives, paper size, paperstrength additives (such as wet and dry additives, permanent pressresins, porosity control, precoated for coated paper, primer forprinting, protective coating, replacement for latex as an internalbinder in all applications, sealants, stain resistance, surfacemodifiers for wood, metals and glass, textile strength, textile wetprocessing aids, and water resistance/repellency.

[0149] The aqueous compositions of the present invention are highlysuitable for coating physiological substrates (e.g., nails and hair),porous substrates (e.g., wood and paper), cellulose substrates,textiles, and building materials (e.g., ceiling tiles, wall boards,sheet rocks, metals and the like).

[0150] The coating compositions of the present invention providescratch, water and stain resistance, as well as other properties, suchas maintaining flexibility, providing cuttability, durability, desiredfinished color, and resistance to aqueous liquids.

[0151] The aqueous composition of the present invention can also be usedin dye fixatives, adhesives, sealants, cellulosic products to providestrength and/or texture. Examples of cellulosic products include, butare not limited to, ceiling tiles, paper products, non-woven productssuch as sheets, and paint. Non-woven products such as sheets can benatural are synthetic. Examples of non-woven products such as sheetsinclude, but are not limited to, disposable diapers, disposable medicalproducts, and absorbent pads.

[0152] The cellulosic product of the present invention preferablycomprises a cured composition comprising components (A) and (B) in theamount of up to about 10% dry weight, more preferably about 0.005% toabout 2% dry weight.

[0153] The ceiling tile of the present invention preferably comprises acured composition comprising components (A) and (B) in the amount of upto about 20% dry weight, more preferably about 0.005% to about 2% dryweight.

[0154] The non-woven product of the present invention preferablycomprises a cured composition comprising components (A) and (B) in theamount of up to about 20% dry weight, more preferably about 0.005% toabout 15% dry weight.

[0155] The paint product of the present invention preferably comprises acured composition comprising components (A) and (B) in the amount of upto about 25% dry weight, more preferably up to about 20% dry weight.

[0156] Uses of Composition in Metal Conversion Coatings

[0157] Although metal conversion coatings are generally known in theart, traditional chromate coatings have become uneconomical due toincreased costs associated with industrial pollution concerns.

[0158] The compositions of the present invention are very suitable foruse as chromium-free conversion coatings for metal surfaces, for exampleto improve corrosion resistance and adhesion of later-applied coatingson metals such as steel, galvanized steel, aluminum, zinc-aluminumcoated steel and aluminum alloys. Such later-applied coatings caninclude paints, inks, lacquers, plastics and other siccative coatings.The inventive composition can be applied as an aqueous solution and canbe used alone or with additives such as one or more of acetic acid,glycolic acid, and fluoacids such as dihydrohexafluotitanic acid,dihydrohexafluosilicic acid, dihydrohexafluozirconic acid, and fluoboricacid.

[0159] The manner of treating a metal surface can include applying anaqueous solution of the composition (e.g., up to about 90% by weight),and drying the composition in place on the surface or rinsing as by awater bath or shower, preferably drying the composition in place on thesurface. An acid can beneficially be supplied in the solution to producea pH of up to about 5. Suitable methods of application include spraying,immersion, flow coating, roll coating, and the like.

[0160] Corrosion resistance of the coated metals can be measured usingthe “Neutral Salt Spray” test; peel resistance can be measured by the“T-Bend” test, “Reverse Impact” test, or “Cross-Hatch” test. The MEK(methyl ethyl ketone) rub test is used to determine whether a paint hasproperly cured on a metal surface. These tests are detailed hereafter inthe Example section.

[0161] Uses of Composition in Oriented Strand Board

[0162] The aqueous composition of the present invention can also be usedin oriented strand board (OSB). “Oriented strand board” refers to acomposite wood product based upon the use of special forms of woodflakes. Flake is a long, flat piece of wood that is about 1 to 4 inches(about 25-100 mm) in length. The length is in the longitudinal (grain)direction; the thickness is 0.010-0.040 inches (0.25-1.00 mm); and thewidth is variable. A flake has a length to thickness ratio of at leastabout 100.

[0163] OSB is produced by mixing dried flakes, or strands with resinadhesive, wax and other additives, and then forming the strands intomats on a wide screen caul. The strands are oriented in specificdirections. The mat is then pressed, at temperatures up to about 218° C.(See Kirk-Othemer, Encyclopedia at Chemical Technology, Fourth Edition,Supplement Volume, J. Wiley ad Sons, (New York, 1998, pp 803-807).)

[0164] OSB is a reconstituted wood product. It provides a lower costalternative to plywood and solid sawn wood and can be produced in a widerange of densities.

[0165] The pH of the emulsion used in oriented strand boards is at leastabout 4, preferably at least about 7.5, more preferably from about 8.8to 11.5, and most preferably about 10.2.

[0166] Uses of Composition in Cellulosic Products

[0167] As used herein, “cellulosic products” is intended to refer toproducts containing cellulosic fibers, such as paper, paper board,cardboard and any related product. The following discussion concerningpaper is illustrative and applies to all related materials andprocesses.

[0168] Paper is made by a process that includes preparing a paper makingpulp or slurry, followed by forming the pulp or slurry into a membranefrom which the paper sheet is eventually formed. The wet part (as thisterm is used herein) of the process includes all the stages in furnishpreparation, including pulp blending and refining, through thick stockand thin stock blending, chemical additions and dilutions with bothwhite water and fresh incoming water, to the point of deposition offiber and membrane formation on the wire, at the wet end of the papermaking process. Thus, the wet part of the process includes all stages ofthe paper making process through the formation of the sheet.

[0169] In the papermaking industry, it is common to attempt to optimizepaper making compositions in order to provide specific functionalproperties as efficiently and economically as possible. Suchoptimization can include the addition of compounds to any part of thewet portion of the process, as well as to any other portion of theprocess, including the formed or forming pulp as well as formed orforming paper. Typical compositions include (internal and external)sizing agents (materials) and wet and/or dry strength resins. As usedherein, internal sizing refers to sizing associated with the addition ofsize at the wet part of the paper making process, and thus internalsizing or sizing at the wet part of the paper making process refers tothe addition of size at any of the stages of the wet part of theprocess. Surface sizing refers to the addition of materials to theformed or forming pulp as well as formed or forming paper.

[0170] Wet and/or dry strength resins are a common additive to papermaking compositions. These materials act to provide strength to wetpaper and are used in, among other paper products, paper towel andpackaging. Among other uses, they are also useful as creping adhesives.Wet strength resins may be added during paper production to bind thecellulose fibers together, and to enhance the strength of the paperproduced so that the paper does not fall apart when used under wetconditions. Wet and dry strength resins may be added during any part ofthe paper making process including the wet part or may be added toformed pulp and formed paper.

[0171] Use of Composition as Coating for Ceiling Tiles

[0172] The coating of the present invention is highly suitable forceiling boards (ceiling tiles), since the coating gives the coated boardan improved face durability and cuttability. Although the coating can beused on a ceiling board of any suitable composition, the boards forwhich the present coating compositions have been found to be suitablecomprise fiber in an amount in the range of from about 5 to about 85% byweight, filler in an amount in the range of from about 5 to about 90% byweight, and a binder in an amount in the range of from about 1 to about25% by weight. Preferably, the board is an acoustical board comprisingfiber in an amount in the range of from about 20% to about 80% byweight, filler in an amount in the range of from about 20 to about 75%by weight, and a binder in an amount in the range of from about 1 toabout 20% by weight. In some aspects, the acoustical board comprisesfrom about 10 to about 80% by weight of a fiber selected from at leastone of mineral wool and cellulosic fibers, a filler at an amount in therange of from about 5 to about 90% by weight, said filler being selectedfrom the group consisting of perlite and clay, and an organic binder atan amount in the range of from about 1 to about 20% by weight.

[0173] Some suitable acoustical boards which can be coated with thecompositions described herein are described in and can be prepared inaccordance with procedures described in U.S. Pat. No. 4,963,603 toFELEGI et al., assigned to Armstrong World Industries, Inc., whichpatent is hereby incorporated by reference as though set forth in fullherein.

[0174] Coatings that produce an “I beam” effect with such board areprovided in accordance with preferred embodiments of the presentinvention. The invention provides a surface treatment to the board tomake the surface strong, but also pliable when the board is cut. In someaspects, the “I beam” effect results from configurations wherein eachmajor surface of the board, such as two faces, are coated with acomposition of the invention, leaving uncoated porous board material,such as that described above, therebetween.

[0175] While ceiling tile and wallboard material are typical of thebuilding materials contemplated herein, these materials are consideredto be representative of one type of substrate which is suitable to becoated by the compositions of the invention. Therefore, for ease ofdiscussion, reference is made herein to ceiling tile, and in particular,acoustical ceiling tile; however, it will be readily understood thatother substrates are similar, and all such materials are intended to bewithin the scope of the present invention.

[0176] Use of Composition as Coating for Porous Substrates

[0177] The coating compositions of the present invention areparticularly suitable for porous substrates. This is especially the casein applications where it is desired to coat a porous substrate withoutsubstantially reducing the porosity of the substrate.

[0178] The coatings of the invention have particular utility in coatingsubstrates having a porosity of at least about 50-95%, preferably about85%-90%, based on the amount of air voids. Thus, for a substrate havinga porosity of 90%, 90% of the substrate volume is made up of air holeswhile 10% is solid components. Preferably such substrates areopen-celled.

[0179] Preferably, the compositions of the invention reduce the porosityof the substrate upon coating and curing by less than about 10%, morepreferably less than about 5%, more preferably, less than about 2%, andmost preferably less than about 0.5%.

[0180] Reduction in porosity can be measured by running an NRC test(described in the test section (Reverberation Room Sound AbsorptionTest) below) and determining the change after a coating of the inventionhas been applied to a substrate and cured. Using this test, thecompositions of the invention should not change the rounded NRC numberof substrates coated with compositions of the invention and cured, bymore than about 15, in comparison with the uncoated substrate.

[0181] As discussed herein, certain properties are desirable withrespect to building materials in general, as can be specificallyillustrated with ceiling tiles in particular. For finished ceiling tile,these properties include the following:

[0182] Acoustical: the ability of the ceiling tile to control sound inand between rooms. The acoustical properties are measured in three waysCAC (Two room transmission loss), NRC (Reverberation room soundabsorption), & AC (open room sound attenuation)

[0183] Color: typically white as the color and measured using the L andb color scales. L being the scale from black to white and b being thescale from blue to yellow. The instrument used to color measurement isthe Hunter color meter, i.e. a Hunter Miniscan® 45/O-L Hunter AssociatesLaboratories, Reston, Va.

[0184] Face Durability: the ability of the surface of the board toresist scratches, and damage during normal installation and servicingthe plenum. Measured by scrubbability, finger scratch resistance (i.e.,Hess Rake test), and taber abrasion, all of which tests are described indetail in the section entitled “Standard Test Procedures Used inExamples”.

[0185] Substrates coated with compositions of the invention and curedexhibit a Hess Rake value of at least about 8, preferably at least about10, more preferably at least about 12, and most preferably at leastabout 14.

[0186] Substrates coated with compositions of the invention and curedexhibit a Taber Abrasion loss value of less than about 1 gram,preferably less than about 0.6 grams, more preferably less than about0.4 grams, and most preferably less than about 0.2 grams.

[0187] Cuttability: The ease of the knife to cut through the boardwithout chipping or flaking the coating. This is measured by thecuttability test. In this test, a straight cut is made in the center ofthe ceiling tile using a sharp razor blade. The cut is then covered witha 6 inch long piece of tape, having a width of 2″, such that the lengthof the tape is aligned with the length of the cut and such that thewidth of the tape completely covers the cut, making sure to cover theend of the cut where the knife was withdrawn from the cut. The tape isthen peeled off manually, while maintaining the rate of peel at aconstant speed, and the number of paint chips which develop are counted.A cuttability number is then calculated: (# flakes/sq. inch)×10. Thistest simulates a tegular cut made during a field installation of aceiling tile system—the lower the number, the better. Substrates, coatedwith a composition of the invention which is then cured, exhibit acuttability value of less than about 15, preferably less than about 10,more preferably less than about 2 and most preferably less than about 1.

[0188] Sag: The ability of the board to maintain a flat and even surfacewhen exposed to high humidity conditions. Measured using a controlledhumidity chamber and deflection gage.

[0189] Fire performance: The resistance to flame spread. Measured by30-30 tunnel test.

[0190] The addition of coatings to the substrate are often employed toobtain the desired properties of color, face durability, and fireperformance. However, typically, the properties of acoustics, andcuttability are somewhat diminished once a coating is added.

[0191] Common practice has been to add fillers to the coatings to giveproperties of face durability, color and fire performance. However, ahigh amount of fillers (for example, 40% or greater by weight) willtypically form a plate-like sealed surface on the board, which isdesirable for face durability but will hurt the acoustical properties.They also prevent the coating from soaking into the board, and cause thepaint to chip when a cut is made. Fillers also serve to “hide” the colorof the substrate (in many compositions, the binder itself will not hidethe substrate).

[0192] It has been unexpectedly discovered that compositions of thepresent invention achieve improved face durability while adding littleor no fillers, such as the additives discussed above to the coating. Asused herein, the term “little or no fillers” is intended to includecompositions having less than about 15% fillers, more preferably, lessthan about 1%, based on the total weight of the composition. Ideally,the compositions of the invention have substantially no fillers. Sincelittle or no fillers are added, the viscosity of the coating remains lowand thus the coating is allowed to penetrate and soak into the board.This effect has been observed in accordance with the present inventionto be more of a thin and diluted coating, instead of a formed, “plated”coating. In other words, coatings of the invention penetrate porousstructures rather than “plating” across the surface, such as by platingacross openings. This keeps the “openness” of the surface of the boardintact and does not diminish the acoustical properties of the substrate(or ceiling tile). The coating also gives enough “hiding power” to coverthe color of the substrate upon subsequent application of a finishcoating, such as a paint, even with little or no fillers. Thus,preferably, the coating may be clear in color, not significantly affectacoustics upon curing, but still provide enough of a coating effect sothat subsequently applied coatings of, for example, paints so that thepaint can cover and hide the color of the substrate.

[0193] Coating compositions of the invention preferably have arelatively low viscosity. In some aspects, coating compositions of theinvention have a viscosity of 100 cps or less, preferably 50 cps, orless and most preferably 35 cps or less, as measured on a Brookfieldviscosimeter using a No. 1 spindle, unless otherwise specified inspecific example, at a temperature of 25° C. and spindle speed of 100rpm to standard depth on the spindle.

[0194] It has been found that component (A) forms a clear coating whichenables subsequent finish coats to hide the color of the substrate. Thishas been shown to be the case with HERCOBOND 5100® as component (A).HERCOBOND 2000®, HERCOBOND 1000® and HERCOBOND 5100®, alone or incombination with each other have also been found to form a clear coatingwhich enables subsequent finish coats to hide the color of thesubstrate.

[0195] In some aspects, compositions of the invention provide coatingswherein the L and b values (L and b being discussed in the “colorsection” above) are substantially unchanged after application of thecoating to the substrate followed by curing of the coating. By“substantially unchanged” in reference to L and b values herein is meantthat the L value changes by less than about 5, preferably less thanabout 1; and the b value changes less than about 1, preferably less thanabout 0.1.

[0196] Advantages

[0197] The unexpectedly superior spectrum of properties provided by thecompositions of the invention is more favorable than that which would beexpected to be supplied by each component, separately, particularly inview of the fact that the resultant composition exhibits positiveaspects of each the components, while certain negative aspects thatwould be expected by the use of each component, separately, are notexhibited.

[0198] In developing the invention, different compositions wereattempted, including compositions of component (A) such aspolyamidoamine-based compositions (without being combined with acopolymer of an alkyl chloride and a polyalkene); and includingcompositions of component (B), such as those based on emulsions ofcopolymers of alkyl chloride and polyalkene (without being combined witha polyamidoamide).

[0199] In particular, in experiments involving treating buildingmaterial substrates with compositions comprising components (A) or (B)it was found that compositions based on emulsions of copolymers of alkylchloride and alkenes, such as copolymers of vinyl chloride and ethylene,provided very good cuttability and no flaking or chipping; however,these compositions did not achieve the desired finished color in ceilingtile application (for example, there was no holdout from the primecoat,i.e., they did not hide the color of the substrate). Similarly,polyamidoamine-based compositions provided very good scratch durabilityand finish color, but provided poor results with regard to cutting orflaking. It was expected that these negative or poor aspects of theindividual components would be retained by the combined composition.However, contrary to expectations, these poor aspects were notexhibited, but the desirable aspects were retained.

[0200] Primer Coatings

[0201] The compositions of the invention have particular utility as aprimer coating, such as coatings which are applied to anewly-manufactured substrate. The primer coated substrates can thenlater be painted or further coated, either prior to or subsequent toinstallation.

[0202] Application of Composition

[0203] The compositions of the invention may be applied to substrates inany suitable way, such as by coating equipment, including spraying,brushing, roller application, and the like. Those of ordinary skill inthe art can readily select a suitable application system. For buildingmaterials in general and ceiling tile in particular, the substrates maypreferably be coated by spraying. Compositions of the invention may beapplied in any amount suitable for the particular application. Forceiling tile, amounts in a range of from about 5 to about 50 grams ofcomposition/square foot are suitable, preferably amounts of from about10 to about 40 g/square foot, more preferably about 15 to about 25g/square foot. 20 grams of coating composition per square foot ofsubstrate has been found to be particularly suitable amount ofapplication in accordance with the invention.

[0204] After application to the substrate, compositions of the inventionmay be preferably subjected to accelerated drying and curing. Anysuitable drying arrangement may be employed to cure the coating. Theonly requirement is that the water be driven off so that curing takesplace. The coated substrate may be dried in a drying oven at atemperature in the range of about 350° F. to about 460° F., preferably350° to about 450° F. A temperature of about 450° F. has been found tobe particularly suitable. Alternatives such as heat lamps without theuse of specialized drying ovens may be employed alternatively, or inaddition thereto.

[0205] The compositions of the invention exhibit stability over time.Thus, the compositions of the invention do not gel when stored at roomtemperature (20° C.) in a closed, sealed container for a period of atleast about 2 weeks; preferably at least about 1 month.

[0206] Uses of Composition Other than Coating Composition

[0207] The composition of the present invention can also be used asbinders, e.g., to adhere pigments in coating formation to the surface ofpapers. In addition, the use of the binders also provides cohesivestrength to the pigment.

[0208] Preferably, when used as a binder, the composition of the presentinvention is an emulsion and has a ratio of component (A) to component(B) preferably from about 5:1 to about 1:5, more preferably from about2:1 to about 1:1, and most preferably from about 169:1.

[0209] The pH of the emulsion is preferably greater than about 3, morepreferably greater than about 6, and most preferably greater than about7.5.

[0210] Without further elaboration, it is believed that one skilled inthe art can, using the preceding description, utilize the presentinvention to its fullest extent.

[0211] The following preferred specific embodiments are, therefore, tobe construed as merely illustrative, and not limitative of the remainderof the disclosure in any way whatsoever. In the following examples, alltemperatures are set forth uncorrected in degrees Fahrenheit; unlessotherwise indicated, all parts and percentages are by weight.

EXAMPLES

[0212] The following experiments are conducted in an effort to (1)improve the characteristics of building materials, in particular,resistance to water penetration; (2) improve properties of orientedstrand board; (3) improve binding and adhesive strength properties ofpaper coatings; (4) test efficacy of different latices that could beused in the composition of the present invention; and (5) improve metalcoatings. Test procedures for all tests referenced in this specificationare also set forth following the report of the resultant data, at theend of the following Examples.

[0213] The tests were conducted on boards formed in accordance withprocedures for fabricating ceiling boards (tiles). In such tests,coatings of the invention in the form of a prime coat were added to thesubstrate, followed by two coats of finish coating and subsequenttesting. The prime coat is added after it has been textured or designed.This texture can rub off easily so a prime coat is added and evaluated,which provides a reliable indication of the performance of the coatedtile in typical market/installation.

[0214] The following experiments are conducted in an effort to improvethe characteristics of building materials, in particular, facedurability and cuttability. Test procedures for all tests referenced inthis specification are also set forth following the report of theresultant data, at the end of the following Examples.

Example 1 Evaluation of Formulations Containing Different Polymers andLatices

[0215] This example is directed to Samples 1-11 shown in Table 1 below.Specifically, this example illustrates properties of Samples 1-9containing different latices, and Samples 10 and 11 containing differentpolymers.

[0216] Samples 1-9 are Prepared as Follows:

[0217] For Samples 1-9, a one liter of emulsion is prepared by adding42.2 dry g of KYMENE® 557H wet strength resin (obtained from HerculesIncorporated, Wilmington, Del.) to 25 dry g of latex with mechanicalstirring. 62.5 g of demineralized water is added to the emulsion toyield a slightly blue opaque white dispersion. The dispersion is thenallowed to stir for 15 minutes at room temperature.

[0218] Samples 10 and 11 are Prepared as Follows:

[0219] Sample 10 is prepared using the procedures for preparing Samples1-9 with the exception that Reten® 201 (dimethylamine-epichlorohydrinpolymer) obtained from Hercules Incorporated, Delaware is used.

[0220] Sample 11 is prepared using the procedures for preparing Sample10 with the exception that Reten® 203 (polyDADMAC(diallyldimethylammonium chloride)) obtained from Hercules Incorporated,Delaware is used.

[0221] The Brookfield viscosity of each Sample is initially measured andthen measured again after one week (on the eighth day) using theBrookfield programmable LV DV-II and Viscometer Spindle #2, at 60 rpmand 25° C. The viscosity of each sample is recorded in Table 1.

[0222] Dispersion and color of each sample is also initially observedand then observed again after one week (on the eighth day) by naked eyeand recorded in Table 1.

[0223] Application and General Observations for Aluminum and Wood

[0224] A 20-g aliquot of the emulsion of each of Samples 1-11 (preparedas discussed above) is absorbed onto a 4-inch by ½-inch paint roller andapplied to 11 pieces of aluminum and 11 pieces of wood at the rate of0.046 pounds per square meter.

[0225] The aluminum and wood pieces are then cured for 5 minutes at 150°C. The results are shown in Table 1 below. TABLE 1 EVALUATION INFORMULATION OF COMPONENTS (A) AND (B) Total Brookfield Adhesion LatexSolids Viscosity (cps) Comments to Sample Description Type (%) Initial 1wk Dispersion Film Al/Wood 1 Neocar (Union Vinyl Ester/ 14.6 52 47 NoBlue Hue- Opaque Very Carbide) Acrylic Stable strong/Good 2 Res 3077Vinyl 14.6 39 34 Slight Blue Hue- Opaque Good/Good (Rohm &Acetate/Acrylic Stable Haas) 3 Airflex 500 Vinyl 14.6 62 54 BlueHue-Stable Opaque Good/Good (Air Products) Acetate/Ethylene 4 Airflex4514 Vinyl Chloride 14.6 70 53 Very Blue Hue- Clear Good/Good (AirProducts) Amide Stable Terpolymer 5 Airflex 4500 Vinyl Chloride 14.6 7052 Very Blue Hue- Clear Good/Good (Air Products) Amide Stable Terpolymer6 Flexhane 620 Urethane Hybrid 14.6 Agglom. — Agglomerated on — —/— (AirProducts) addition 7 Vinac 884 Vinyl Acetate 14.6 44 40 Slight Blue HueOpaque Good/Good (Air Products) 8 Dow 620 SBR 14.6 62 53 Some PPT BlueClear Good/Good (Dow) Hue 9 Airflex 4530 Polyamidoamine- 14.6 40 37Slight Blue Hue- Opaque Good/Good (Air Products) epihalohydrin andStable ethylene vinyl chloride 10 Airflex 4530 Polyamidoamine- 14.8 74 —Slight Blue Hue- Opaque Fair/— (Air Products) epihalohydrin and Stableethylene vinyl chloride 11 Airflex 4530 Polyamidoamine- 14.8 278 —Slight Blue Hue- Opaque Fair/— (Air Products) epihalohydrin and Stableethylene vinyl chloride

[0226] As shown in Table 1, different latices could be used to producethe composition of the present invention. In particular, with exceptionof Sample 6, all the Samples provide stable dispersion and form films.

Example 2 Application and General Observations for Use of Composition asBinders

[0227] This example illustrates that the composition of the presentinvention has excellent binding properties as compared to conventionalbinding compositions in the art.

[0228] Composition of the Present Invention:

[0229] A one liter of emulsion is prepared by adding 42.2 dry g ofHERCOBOND® 5100 wet strength resin (obtained from Hercules Incorporated,Wilmington, Del.) to 25 dry g of DOW® 620 SBR (obtained from DowChemical Company, Midland, Mich.) with mechanical stirring. 62.5 g ofdemineralized water is added to the emulsion to yield a slightly blueopaque white dispersion. The dispersion is then allowed to stir for 15minutes at room temperature.

[0230] The final product has a total solids of 14.6%.

[0231] Control Composition (Composition of Conventional BindingComposition):

[0232] A control coating formulation is prepared by adding 0.1 part of(0.5 g) sodium polyacrylate dispersant (Dispel N40 obtained from AlliedColloids, Suffolk, Va.) to 102 g of water under agitation. 100 parts ofcalcium carbonate (obtained from Omya Inc., Florence, Vt.), followed bythe addition of 10 parts of a control composition (containing one literof the emulsion prepared as described above (using HERCOBOND® 5100 andDOW® 620) at a reduced agitation rate. 0.3 parts ofcarboxymethylcellulose (CMC 9M31 obtained from Hercules Incorporated,Wilmington, Del.) is added and the mixture is stirred for several hours.

[0233] Brookfield viscosity of both the coating mixtures containing thecomposition of the present invention and the control composition aremeasured using a Brookfield viscometer (which is a product of BrookfieldEngineering, Stoughton, Mass.) using a No. 5 spindle at 100 rpm of thecoatings).

[0234] The Brookfield viscosity of the coating mixture containing thecomposition of the present invention is 234 cps. The Brookfieldviscosity of the coating mixture containing the composition of thecontrol sample is 214 cps.

[0235] Three drops of the coating mixture containing the composition ofthe present invention is placed on a first piece of bleached board. Asecond piece of bleach board is used to cover the first piece ofbleached board to create a sandwich structure. A 5-lb weight is placedon the structure for about 18 hours at ambient temperature.

[0236] Three drops of the coating mixture containing the control sampleis placed on a first piece of bleached board. A second piece of bleachboard is used to cover the first piece of bleached board to create asandwich structure. A 5-lb weight is placed on the structure for about18 hours at ambient temperature.

[0237] Both of the sandwich structure prepared above are then separatedby hand. The structure made with the composition of the presentinvention requires more force to separate. The structure with thecontrol composition is easily separated and has a fragile dried film. Incontrast, the structure with the composition of the present inventionhas excellent adhesive properties. In addition, the film formed by thecomposition of the present invention is not totally dried, and thus haswater-holding properties.

Example 3 Application and General Observations for Use as a ConversionCoating for Metal

[0238] This example is directed to Samples 1-8 in Table 2 below andillustrates Neutral Salt Spray (NSS) performance and physical durabilityof painted metal panels.

[0239] Each of Samples 1-5 is Prepared as Follows:

[0240] A one liter of emulsion is prepared by adding 42.2 dry g ofKYMENE® 557H wet strength resin (obtained from Hercules Incorporated,Wilmington, Del.) to 25 dry g of Airflex® 4530 with mechanical stirring.62.5 g of demineralized water is added to the emulsion to yield aslightly blue opaque white dispersion. The dispersion is then allowed tostir for 15 minutes at room temperature.

[0241] The dispersion has a total solids of 14.6%, pH of 4.5 to 5.0, anda Brookfield viscosity of 28 centipoise at 25° C. (The Brookfieldviscosity is measured using the Brookfield programmable LV DV-II andViscometer Spindle #2, at 60 rpm and 25° C.)

[0242] For each of Samples 1-5, the dispersion (prepared as describedabove) is added to 0.30 weight percent of fluozirconic acid (obtainedfrom Allied Signal). The amount of the dispersion used to prepare eachof Samples 1-5 is: 0.7 weight %, 3.4 weight %, 6.75 weight %, 33.8weight %, and 84.5 weight % (respectively).

[0243] Samples 6-8:

[0244] Sample 6 contains 0.30 weight %. by volume of fluozirconic acid.

[0245] Sample 7 contains 10% by volume of Permatreat 1500 which is achrome no-rinse treatment obtained from BetzDearbom.

[0246] Sample 8 has 15% by volume of Permatreat 1021B which is anon-chrome treatment obtained from BetzDearbom.

[0247] Hot-dipped galvanized metal panels are obtained from ACT Corp andcleaned with BetzDearborn KL4010, a commercial alkaline cleaneravailable from BetzDearbom. The metal panels are rinsed with deionizedwater for 5 seconds, and subsequently coated with Samples 1-8 by spincoat application, followed by forced air drying. Duplicate panels arecoated for each sample.

[0248] The treated panels are painted with a two-coat paint typicallyused in coil applications, available from Akzo-Nobel. The primer and topcoat are applied and cures according to the manufacturersspecifications.

[0249] The coated metal panels then undergo NSS testing, T-Bend,Cross-Hatch, Reverse Impact, and methyl ethyl ketone (MEK) double rubtesting. The metal panels are observed and the results are shown inTables 2 (NSS) and 3 (other test data).

[0250] Neutral salt spray results are reported in Table 2 as scribe,field. In addition, Table 2 recites “/” for results of duplicated metalpanels coated with each sample (as shown in column 5 of Table 2).Results are for duplicate panels and are rated as per ASTM D-1654 (with10 being perfect); T-Bend data describes the tendency for paint todisadhere from a 180° bend in the metal measured according to ASTMD4145-83 (wherein 0T is perfect); Cross-Hatch data describes thetendency to disadhere from areas between closely spaced lines throughthe paint. The test was done dry according to ASTM D3359 (from a 0B to5B scale, wherein 5B is perfect); Reverse Impact data describes thetendency of paint to disadhere from metal deformed by an impact of knownmomentum on the reverse side of the test surface according to ASTMD2794; MEK rub data describe whether the paint is cured properly and isdescribed in National Coil Coaters' Association (NCCA) Method II-18.TABLE 2 NSS data for painted panels Sample 336 Hrs. 500 Hrs. 672 Hrs.840 Hrs. 1000 Hrs. 1 9,9 9,9 7,9 9,7 (4) 7/7,5/7 2 9,9 9,9 8,9 8,8 (6)8/8,8/7 3 10,10 9,10 8,9 7,9 9/9,9/8 4 9,10 9,10 8,8 9,9 7/9,8/7 5 8,107,9 8,9 6,9 5/5,8/9 6 10,10 9,10 9,9 9,9 7/4,5/8 7 10,10 9,10 9,10 9,99/9,9/8 8 10,10 9,10 9,9 10,10 9/9,9/8

[0251] TABLE 3 Physical Durability Rev. Imp. Sample T-Bend Cross-Hatch(In/lb) MEK rubs 1 0T 5B 160160 100+ 2 0T 5B 160 100+ 3 0T 5B 160 100+ 40T 5B 160 100+ 6 1T 5B 160 100+ 7 0T 5B 160 100+ 8 1T 5B 160 100+

Example 4 Application and General Observations for Use as a ConversionCoating for Metal

[0252] This example is directed to Samples 1-4 and 6-8 shown in Table 4below. The procedure for preparing Samples 1-4 is the same as Samples1-4 in Example 3 with the exception that 0.45 weight % of fluozirconicacid is used. Samples 6-8 are prepared using the same procedures forpreparing Samples 6-8 in Example 3. The data in Table 4 is for aone-coat black polyester paint obtained from PPG. TABLE 4 T-Bend ReverseImpact Test Cross-Hatch Test MEK rubs 1000 Hours Neutral Salt (ASTM Test(in/lb, ASTM (NCCA II- Spray* Sample D4145-83) (ASTM D3359) D2754) 18)(ASTM B171654) 1 0T 5B 160 95 1/1, —/— 2 0T 5B 160 100+ 0,0 3 0T 5B 160100+ —/— 4 0T 5B 160 100+ 5/5, 7/4 6 2T 5B 160 44 2/2, 6/6 7 0T 5B 160100+ 7/7, 9/9 8 1T 5B 160 100+ 3/4, 9/8

Example 5

[0253] Evaluation of Potential Materials for Precoat

[0254] The following materials were evaluated:

[0255] KYMENE 557H® (available from Hercules Incorporated, Wilmington,Del.)

[0256] KYMENE 450® (available from Hercules Incorporated, Wilmington,Del.)

[0257] HERCOBOND 1000® (available from Hercules Incorporated,Wilmington, Del.)

[0258] HERCOBOND 2000® (available from Hercules Incorporated,Wilmington, Del.)

[0259] HERCOBOND 5100® (available from Hercules Incorporated,Wilmington, Del.)

[0260] PICCONAL AA101® (thermoplastic resin available from HerculesIncorporated, Wilmington, Del.)

[0261] PICCOTAC 95-55wk® (thermoplastic resin available from HerculesIncorporated, Wilmington, Del.)

[0262] TACCOLYN 5001® (thermoplastic resin available from HerculesIncorporated, Wilmington, Del.)

[0263] AIRFLEX 4530® (available from Air Products and Chemicals,Allentown, Pa.)

[0264] AIRFLEX 320® (available from Air Products and Chemicals,Allentown, Pa.)

[0265] FLEXBOND 325® (available from Air Products and Chemicals,Allentown, Pa.)

[0266] CHARTWELL ® B523.6WH (as an additive, available from Chartwell,International, Attleboro Falls, Mass.)

[0267] HYCAR 26256 (available from BF Goodrich, Ohio)

[0268] AZC (Ammonium Zirconium Carbonate, from Hopton Technologies,Albany, Oreg.).

[0269] LUCIDENE ® 243 (available from Morton International, Chicago,Ill.)

[0270] LUCIDENE ® 245 (available from Morton International, Chicago,Ill.)

[0271] MORKOTE ® 1725 (available from Morton International, Chicago,Ill.)

[0272] TRITON X-100 (available from Union Carbide Chemicals and PlasticsCompany, Incorporated, Danbury, Conn.)

[0273] Testing of the different materials was performed on boards thatwere taken from the production line before the surface was painted withanything but after being textured or designed. The grade used fortesting was standard grade, 0.710 inches thick SAG from the ArmstrongWorld Industries Beaver Falls plant. The boards were then hand sprayedusing the chemicals from the above listing, as described in Table 5,below. After spraying, the boards were put through a fabrication dryerto dry the coating (oven temp range 400-460° F.). The boards were thenfinished with 2 coats of finishing paint (standard water-based paint ofabout 48 wt % solids for finishing ceiling tile) and oven dried at atemperature in the range of 400-460° F., and set aside for testing.

[0274] The testing was directed to three parameters for grading theproducts. They are: scratch test using the HESS rake (also referred toas a finger rake), cut test with a razor knife, and color. The cut andscratch tests are somewhat subjective but provide a very good feel forhow the different products compare. The results are set forth in Table5, below. TABLE 5 Test Scratch Series Experiment No. Product used %Grams applied per sq. ft L b (HESS) cut Comments A 1 Airflex 4530 10 2016 3 Water 52.3 Clay Fillers 36.9 (Control Paint) 2 Airflex 4530 44.4420 20 5 Water 55.31 Triton X-100 0.25 (Airflex Precoat) 3 Flexbond 32544.44 20 18 4 Water 55.31 Triton X-100 0.25 4 Airflex 4530 6 20 16 3Water 48 Clay Fillers 46 5 Piccotac 95-55 wk 100 20 16 3 6 Airflex 453010.5 20 18 3 Water 50.8 Clay Fillers 35.8 Chartwell 3523.6 WH 2.9 7Hycar 26256 44.44 20 20 4 Water 55.31 Triton X-100 0.25 8 Airflex 453010.00 20 16 3 Water 48.40 Clay Fillers 34.20 AZC (Ammonium 4.60Zirconium Carbonate) Chartwell B523.6WH 2.80 9 Airflex 4530 10.3 20 16 3Water 49.8 Clay Fillers 35.1 AZC 4.8 10 Airflex 4530 10.77 20 16 4 Water52.17 Clay Fillers 36.81 Triton X-100 0.25 B 1 Picconal 100 20 20 1 2Lucidene 243 44.44 20 22 4 Water 55.31 Triton X-100 0.25 3 Airflex 453010.8 20 18 3 Water 52.3 Clay Fillers 36.9 (Control) 4 Airflex 4530 42.3220 20-22 5 Water 52.68 Triton X-100 0.24 AZC 4.76 5 Airflex 4530 44.4420 20 5 Water 55.31 Triton X-100 0.25 (Airflex Precoat) 6 Airflex 453010.3 20 16 3 Water 49.8 Clay Fillers 35.1 AZC 4.8 7 Morkote 1725 44.4420 20 4 Water 55.31 Triton X-100 0.25 C 1 Piccotac 100 10 −16 2 2Piccotac 100 20 86.7 2.1 −16 2 3 Taccolyn 100 10 86.7 2.5 −16 2 4Taccolyn 100 20 88.9 1.1 −16 3 5 Picconal 100 10 86.4 2.2 −16 3 6Picconal 100 20 86.7 2.1 −18 3 7 Airflex 4530 44.44 20 88.4 2 20 4 Water55.31 Triton X-100 0.25 8 Kymene 450 100 20 88.8 3.6 −16 3 9 Hercobond5100 100 20 92 1.8 18 3.5 10 Hercobond 1000 100 20 91.7 1.6 −20 3.5 11Hercobond 1000 100 40 93.6 1.3 22 3.5 12 Hercobond 2000 50 40 93.2 1.422 3.5 Water 50 13 Hercobond 1000 50 20 88.9 2.7 −16 4 Kymene 450 50 14Hercobond 2000 16.7 20 90.3 3.9 −18 3 Kymene 450 66.6 Water 16.7 15Hercobond 5100 66.6 20 92.3 1.3 16 3.5 Hercobond 2000 16.7 Water 16.7 D1 Hercobond 5100 99.8 20 91.9 1.8 18 4 Triton X-100 0.2 2 Hercobond 510075 20 91.8 2.1 20 5 Airflex 4530 11.11 Triton X-100 0.06 Water 13.83 3Hercobond 5100 50 20 91.4 1.9 18 * board was wet Airflex 4530 22.22Triton X-100 0.12 Water 27.66 4 Hercobond 5100 25 20 89.4 1.7 18 4Airflex 4530 33.33 Triton X-100 0.18 Water 41.48 5 Water 97 20 91.8 2.7−18 Triton 3

[0275] In the above Table 5, four series of tests (A-D) were conducted;each series being conducted during a separate test session. The firstseries, A, was conducted to evaluate how the material cut (distinct from“cuttability test” discussed elsewhere herein) and to evaluate thespecimen in terms of the HESS rake test.

[0276] The color test was started later, only after initial testingshowed good strength results. In initial tests, although not reflectedin the table, color deviation was not acceptable (e.g., for L, a valueof +/−5 away from the desired standard and for b, a value of +/−1 awayfrom the desired standard), showing poor light reflectance and yellowcolor. The results for the tests should be interpreted as follows:Scratch test (Hess Rake test)—the higher the number the better. Cuttest—the higher the number the better 5 being the best for that seriesand 5 being essentially no chips per square inch, 4 being 1 or 2 chipsper square inch. With respect to color, the goal is to achieve a whitevalue of: L from about 92 to about 93; b of about 1.6 to about 2.4,after application of the finish coats (that is, after application offinish coats over or on top of the coatings of the invention).

[0277] The above data demonstrate that the AIRFLEX precoat (formula A2)provided the best scratch and cut numbers but did not optimize theability of the finish coat to hide the color of the substrate when thefinish coat was applied over the coating of the invention. The HERCOBOND5100® (formula C9) provided good scratch numbers and good color numbers.The most promising results include those at a weight ratio of 75%HERCOBOND 5100® and 11% AIRFLEX 4530®, remainder water and surfactant(formula D2, for example).

[0278] Certain of the resins tried failed due to the high heats used inthe ovens which darkened the boards and the prime coat to the pointwhere the two coats of finishing paint could not hide it. Additionally,certain resins were too brittle after drying to accomplish the goalsgiven. The KYMENE 450® did have color issues as well, and did notperform as well for the strength. The HERCOBOND 2000® gave good resultson the board except for cut, but it was difficult to spray the producton to the board. This property would be expected to be extremelyundesirable from the standpoint of the spray operator. The HERCOBOND1000 gave good results except for cut.

Example 6

[0279] The following illustrates how the coating of the inventionimparts two types of improved durability on ceiling tile product:improved face durability and improved adhesion/cutting/flakingcharacteristics. Face durability is measured by the Hess Rake/Fingerscratch (BF.5), Taber abrasion (A7), Scrubbability (BS.10), and Ballhardness (BH.10) tests. These tests simulate the repetitive motion ofmoving ceiling tiles out of the grid for access to heating, ventilation,electrical systems, and plumbing. Adhesion/cutting/flaking is measuredby cuttability test or the six inch tape test, discussed above.

[0280] As shown in Example 5, the coatings of the invention weredeveloped from coating systems which showed promise in lab testing. Onetype of coating (A2), was a dilute penetrant solution of AIRFLEX 4530®,water, and TRITON X-100®. As shown in Example 5, this coating providedgood face strength durability and cutting, but poor color numbers (L andb values). Another coating was non-diluted HERCOBOND 5100®. This coatingprovided good face strength durability and color numbers, but poorercutting characteristics. The two different chemistries were thencombined. It was found that at a weight ratio of 75% HERCOBOND 5100® and11% AIRFLEX 4530® (remainder surfactant and water, formula D2), optimumface durability, cuttability and color numbers were achieved.

[0281] The data below are for coating samples of the invention that wereprime coated in laboratory conditions and finished under normalmanufacturing conditions (i.e., at the Armstrong World Industries,Beaver Falls commercial plant). Sanded, dry material from the wet endwere cut down into 2 ft×2 ft samples and then, after being designed,hand sprayed with 20 g/sqft of the coating. The coating was applied inplace of a normal prime coat. The boards were then dried in fabricationovens (400-460° F.), and coated as normal on-line with two coats offinish paint. The results are set forth in Table 6. TABLE 6 ControlPrime Coat¹ Test Coating² Hess Rake Test 16   20 Cuttability 16.7 3.3Small Scale Fire Pass Pass (Ring Test) Loss On Ignition Pass PassVolatiles Pass Pass Specific Gravity Pass Pass

[0282] The samples were then further tested by different personnel. Theresults are set forth in Table 7. TABLE 7 Normal prime coat¹ TestCoating² Taber Abrasion 0.7078 0.0280 Hess Rake 12 16 Scrubbability 6 10Ball Hardness 68 71

Example 7

[0283] The next example illustrates scale-up for a capability study. Forthis test, the coating was substituted in place of a conventional primepaint on a production line. The coating was sprayed onto the board anddried on-line, then finished as normal on the fabrication line. Thecoating formulation was the same as in the lab scale tests—75% HERCOBOND5100®, 11.11% AIRFLEX 4530®, 0.06% TRITON X-100®, and 13.83% water. Theapplication rates were as follows:

[0284] Test Material—20 g/sqft coating of the invention, prepared bymixing at room temperature in a 150 gal mixer the components of formulaD2 to make 100 gals total, 48 g/sqft finish paint

[0285] Control Material—20 g/sqft prime paint, 43 g/sqft finish paint

[0286] Again, improved face durability and cuttability were achieved, asindicated in Table 8: TABLE 8 Control material¹ Test Material² TaberAbrasion 0.0347 0.0251 Hess Rake 12 16 Ball Hardness 82.0 79.2Scrubbability 63 87 Cuttability 7.5 0.8

Example 8

[0287] This example illustrates that the coatings of the invention canbe applied to a porous type fiber substrate (such as a ceiling tile) andimpart durability properties to that substrate without sealing it off,losing porous properties (such as acoustics) or detracting from theaesthetics, while still maintaining a Class A fire performance, and yetnot undesirably impacting the sag performance of the tile. Acousticproperties were measured by CAC (AL20), NRC (AL10), and AC (AL60) tests,while fire properties were measured by a 30/30 Tunnel test (A5.21). Theresults are set forth in Table 9. TABLE 9 Control Material¹ TestMaterial² NRC (4 frequency average) 0.75 (0.755) 0.75 (0.755) CAC 36 36AC (OPL) 180 170 Flame Spread Rating 11.5 17.3 Sag −75 (mils) −53 (mils)

[0288] Without intending to be bound by theory, it is believed thatthese values are accomplished because of the low solids level in thecoatings, along with the crosslinking capability of the HERCOBOND 5100®under heat. The low solids level allows the coating to soak into thesubstrate, giving good adhesion/cuttability, yet does not hinder theacoustics of the material. The HERCOBOND 5100® alone crosslinks withitself under heat to form a rigid durable layer. By adding a smallamount of modifier, such as AIRFLEX 4530® to the coating, it is believedthat the amount of HERCOBOND 5100® crosslinking is hindered, providingflexibility and better cutting/flaking properties. The physicalproperties of representative coatings are set forth in Table 10: TABLE10 Loss on Ignition 100% Percent Solids 15.6% Percent Volatiles 84.4%Weight per Gallon 7.91 lbs Specific Gravity 0.94

Example 9 Flexibility Test

[0289] A composition of the invention (D2 in TABLE 5) was prepared. 50 gof the composition was poured onto the interior bottom surface of analuminum pie pan (9″diameter). The pie pan was then placed in a dryingoven for a sufficient period of time to drive off all of the watermoisture at that temperature (about 3 hours). The resultant curedcoating on the bottom of the pan had a thickness of about 5-10 mils andwas firmly adhered to the bottom of the pan.

[0290] The pan with coating adhered thereto was then bent back uponitself so that the bend in bottom of the pan had an overall angle ofsubstantially about 180°. At this extent of bending, the coating hadstill not delaminated or otherwise separated from the pan, and thecoating exhibited substantially no visible cracking. The pan was thenre-flattened and the bend was continued until the pan was again bent180° from the flat configuration, in the direction opposite that of thefirst 180° bend (thus the total excursion, combining both bends wassubstantially 360°). Again, the coating had still not delaminated orotherwise separated from the pan, and the coating exhibited no visiblecracking.

[0291] It was possible to cut the coating with a knife and separate cutpieces from the remainder in the pan by prying the coating up with theknife.

Standard Test Procedures Used In Examples

[0292] Reverberation Room Sound Absorption (A110) References: ANSI/ASTMC 423-90a, B 122, E 548, B 795; ANSI Standard S 1.6, S 1.26, S 1.11, ISOR 354-1963. Purpose: To determine the ability of a test specimen toabsorb sound in a laboratory control and reverberant and diffuseenvironment.

[0293] Sample Preparation:

[0294] Employ sufficient material for at least 8′×8′ ceilinginstallation. Wall materials should be a sufficient amount to install ina 7.5′×9′ area when the samples are 30″ wide or an 8′ by 9′ area whenthe samples are 24″ wide. Samples smaller than 46 ft² are not to beemployed for this test.

[0295] Test Parameters:

[0296] The type of mounting(s) employed should be consistent betweensamples. The following mounting systems may be employed, as long asconsistent between samples being prepared:

[0297] E-400 Mounting−16″ airspace behind sample.

[0298] Results:

[0299] NRC (Noise Reduction Coefficient) which is the single numberdetermined by averaging the absorption coefficients at 250 Hz, 500 Hz,1000 Hz, and 2000 Hz and rounding to the nearest 0.05. The absorptioncoefficients at ⅓ octave intervals between 100 Hz and 5000 Hz. When thespecimen is a number of objects, such as free-standing screens orbaffles, the results are reported in Sabius Per Unit.

[0300] Two Room Transmission Loss (A120) References: ASTM Designation: E1414-91a, C 423, C 634, C636, E 90, E 336, E 413, E 548, E 717; ANSIStandard S 1.11-1986; AMA 1-II-1967 Purpose: To measure soundattenuation provided by a suspended ceiling in the presence of acontinuous plenum space under prescribed laboratory conditions.

[0301] Sample Preparation:

[0302] Sufficient material to install in two test rooms ofapproximately:

[0303] 416 sq. ft. for 2×2 boards

[0304] 448 sq. ft. for 2×4 boards

[0305] 37.5 sq. meters for 600×600 boards

[0306] 40.5 sq. meters for 600×1200 boards

[0307] Test Parameters:

[0308] The type of grid is to be consistent between samples. Thestandard grid types are:

[0309] {fraction (15/16)}″ T-Bar

[0310] {fraction (9/16)}″ T-Bar

[0311] Metric Wide and Metric Narrow

[0312] Bolt Slot

[0313] Results:

[0314] The normalized attenuation values at each ⅓ octave band to thenearest 1 dB. The total number of deficiencies from the criterion curveand the calculated CAC value obtained from the test are reported.

[0315] Open Plan Sound Attenuation (A160) References: ASTM Designation:E 1111-88, E 1375-90, E 1376-90, C 423, C 634, E 795, E 1110, E 1130, E1179; ANSI Standards S 1.4, S 1.6, S 1.11, S 1.12 Purpose: Toobjectively measure the specimen's ability to attenuate sound in an openplan space.

[0316] Sample Preparation:

[0317] 1. Furniture Panel: The sample height should be at least 5 feethigh and no greater than 8 feet high. The width of the sample should beat least 2 times the height but no greater than 20 feet wide. Supportsfor the sample and joint details should be consistent between samples.

[0318] 2. Wall Finishes: Sufficient material to cover a 9 feet high by10 feet wide hard reflecting surface is required. The mounting methodshould be consistent between samples. Sufficient fiberglass material tobe installed in the ceiling of the test space to a thickness of 6 inchesmay be employed, if consistent between samples.

[0319] 3. Ceilings: A minimum amount of material to cover a 15 feet by30 feet area is required. In some cases, a 20 feet×30 feet area may berequired.

[0320] Results:

[0321] The measured interzone attenuations to the nearest 1 dB for allpositions and frequencies examined. The normal interzone attenuationsand the Articulation Class values will be reported.

[0322] Sag—Standard Cycle (BS. 5) References: New Method PendingPurpose: To determine the effects of humidity, temperature, and gravityon the deformation characteristics of ceiling materials in aninstallation position.

[0323] Sample Preparation:

[0324] Employ three 2 ft×4 ft specimens; four 2 ft by 4 ft specimens forface-up testing.

[0325] Test Parameters:

[0326] Boards are placed in a face down position.

[0327] One cycle consists of 17 hr @ 82 F/90% RH and 6 hr @ 82 F/35% RH.

[0328] Center point deflection is measured initially and after eachsegment of the cycle.

[0329] Typically, four sag cycles run per week.

[0330] Boards may be subjected to multiple cycles if consistent betweensamples

[0331] Inverted sag testing (face-up) is available if consistent betweensamples

[0332] Three determinations

[0333] Estimated Time:

[0334] Elapsed Time=3 days.

[0335] Results: Initial, Hot-Wet, Final deflection readings (mil) andvector data if face up testing is required. RH data throughout the cyclemay also be tracked.

[0336] Scrubbability (BS.10) References: Federal Standard 141A, Method6142; MEP 138 R.1 Purpose: To measure the resistance of a coating, suchas paint on a ceiling tile, to hand washing by a consumer.

[0337] Sample Preparation: Submit one 12″×12″ specimen.

[0338] Test Parameters:

[0339] Sample is cut to fit the Gardner Straight Line WashabilityMachine.

[0340] A hard bristle brush is used to scrub the board.

[0341] A 0.5% solution of Ivory Flakes is used to keep the board wetduring the test.

[0342] The number of cycles at the first sign of breakthrough isrecorded.

[0343] The test is continued until 50% failure or 150 cycles, whicheveroccurs first.

[0344] One determination: 17 inches long×7 inches wide hexagonalspecimen.

[0345] Results:

[0346] Number of cycles to initial breakthrough, total number of cycles,and visual specimen evaluation as per the following rating system: NoBreaks = 0% = A Slight = 0-10% = B Moderate = 10-25% = C Extensive =25-50% = D Very Extensive = 50-100% = E

[0347] Finger Scratch Resistance (BF.5) (Hess Rake Test) References: TM334 Purpose: To determine the durability/damage resistance of paintsystems or surface treatments applied to ceiling materials.

[0348] Sample Preparation: Submit one 2½ inch×8 inch specimen.

[0349] Test Parameters:

[0350] A “Hess Rake” is employed, which comprises 5 spring steel tinesor fingers configured generally in a rake-like fashion. Each tine has adifferent thickness, measured and reported in mils, and has a roundedend and generally rounded cross-section, and is generally. fingershaped. The rake is suspended on a track above the sample so that thetips of the tines barely touch the sample and the rake is then movedalong the track so that tips of the tines are dragged along the surfaceof the sample with slight pressure on the surface.

[0351] Observations are made for initial paint breakthrough.

[0352] Results:

[0353] Thinnest finger at which paint breakthrough occurs (reported inmils corresponding to the diameter of the particular finger) is the HessRake value. The higher the number, the better.

[0354] Hardness—Acoustical Products (BH.10) References: ASTM C 367Purpose: To determine the ability of ceiling panels to resistindentation caused by impacts.

[0355] Sample Preparation: Submit five 4″×4″ specimens or one 12″ by12″.

[0356] Test Parameters:

[0357] A specimen is placed flat under the penetrator of the testmachine (universal test machine, Instron Corporation, Canton, Mass.).

[0358] A 2″ diameter steel ball is forced into the surface of thespecimen to a depth of 0.25″ at a rate of 0.10″/min.

[0359] The load at this point is recorded as the hardness of thespecimen.

[0360] Results:

[0361] Hardness (1b).

[0362] NOTE: Only specimens of the same thickness may be directlycompared, since hardness varies with thickness.

[0363] Tunnel Test 30-30 (AS.21) References: TM 179 R.4 Purpose: Todetermine the surface flame spread characteristics of materials.

[0364] Sample Preparation: Submit three 3¼″×29⅞″ specimens.

[0365] Test Parameters:

[0366] The specimen is placed face down at an angle of 30 degrees andexposed to the open flame of a bunsen burner located at the lower faceof the test specimen.

[0367] Estimated Time:

[0368] Elapsed Time=2 days

[0369] Results: Flame Spread Rating.

[0370] Taber Abrasion Test References: TM 191 Purpose: To obtain theresistance of a given material to abrasion. Sample: Submit one 4.5″diameter disc; Die Cut. (drill ¼″ diameter hole in the center of hardmaterials.)

[0371] Test parameters:

[0372] Number of revolutions (standard=1000 rev).

[0373] Weight (250, 500, or 1000 grams) (uniform between samples).

[0374] Type of abrasive wheel (uniform between samples).

[0375] Estimated Time:

[0376] Elapsed Time=15 min/material (based 1000 revolutions).

[0377] Results:

[0378] Weight Loss (reported in grams lost).

[0379] From the foregoing description, one skilled in the art can easilyascertain the essential characteristics of this invention, and withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various usages andconditions.

What is claimed is:
 1. An aqueous composition comprising: (A) at leastone water-soluble component comprising at least one functional groupthat undergoes a crosslinking reaction; and (B) at least onefilm-forming polymer.
 2. The composition of claim 1 wherein component(A) is selected from at least one of acrylamide-based crosslinkablepolymers, polyamidoamine-epihalohydrin resins, polyamines, andpolyimines.
 3. The composition of claim 2 wherein component (A)comprises acrylamide-based crosslinkable polymers.
 4. The composition ofclaim 3 wherein component (A) comprises cationic functionalizedpolyacrylamides.
 5. The composition of claim 2 wherein the functionalgroup of component (A) is selected from at least one of epoxy,azetidinium, aldehyde, carboxyl group, acrylate and derivatives thereof,acrylamide and derivatives thereof, and quaternary amine.
 6. Thecomposition of claim 5 wherein the functional group of component (A) isselected from at least one of epoxy and azetidinium.
 7. The compositionof claim 2 wherein the film-forming polymer is selected from at leastone polymer derived from monomers of alkyl halides of from 2-12 C atoms,alkene halides of from 2-12 C atoms, alkyl acrylamides of from 2-12 Catoms, alkene acrylamides of from 2-12 C atoms, alkyl acrylates of from2-12 C atoms, and alkene acrylates of from 2-12 C atoms.
 8. Thecomposition of claim 7 wherein the film-forming polymer is selected fromat least one polymer derived from at least one monomer selected from atleast one of styrene, dimethylstyrene, vinyltoluene, chloroprene,butadiene, ethylene, acrylamide, acrylonitrile, acrolein,methylacrylate, ethylacrylate, acrylic acid, methacrylic acid, methylmethacrylate, n-butyl acrylate, vinylidene chloride, vinyl ester, vinylchloride, vinyl acetate, acrylated urethane, hydroxyethyl acrylate,dimethylaminoethyleneacrylate, and vinyl acetate.
 9. The composition ofclaim 2 wherein the film-forming polymer is a latex selected from atleast one polymer derived from at least one monomer comprising repeatingunits derived from an alkyl halide having at least one double bond andan alkene, wherein the alkyl halide has from 2 to 12 C atoms, andwherein the alkene has from 2 to 12 C atoms.
 10. The composition ofclaim 9 wherein the alkyl halide comprises a vinyl halide.
 11. Thecomposition of claim 10 wherein the alkyl halide comprises a vinylhalide and the alkene comprises an olefin.
 12. The composition of claim9, wherein the alkyl halide comprises a vinyl halide and the alkenecomprises ethylene.
 13. The composition of claim 12, wherein the vinylhalide comprises vinyl chloride.
 14. The composition of claim 13,wherein the alkyl halide comprises a vinyl chloride and the alkenecomprises ethylene.
 15. The composition of claim 7 wherein the dryweight ratio of (A) to (B) is about 5:1 to 1:1.
 16. The composition ofclaim 15 wherein the dry weight ratio of (A) to (B) is about 2:1 to 1:1.17. The composition of claim 16 wherein the dry weight ratio of (A) to(B) is about 1.69:1.
 18. The composition of claim 7 further comprising afluoacid.
 19. The composition of claim 15 further comprising a fluoacid.20. A substrate coated with a cured composition of claim
 1. 21. Asubstrate coated with the composition of claim
 2. 22. A metal substratecoated with a cured composition of claim
 18. 23. The metal substrate ofclaim 22, wherein the fluoacid is selected from at least one offluotitanic acid and fluozirconic acid.
 24. The metal substrate of claim23, wherein a cured composition has a pH from about 1.5 to about 5.0.25. A metal substrate coated with a cured composition of claim
 19. 26.The metal substrate of claim 25, wherein the fluoacid is selected fromat least one of fluotitanic acid and fluozirconic acid.
 27. The metalsubstrate of claim 26, wherein a cured composition has a pH from about1.5 to about 5.0.
 28. A cellulosic product comprising a curedcomposition of claim
 1. 29. A cellulosic product comprising a curedcomposition of claim
 2. 30. A ceiling tile comprising a curedcomposition of claim
 1. 31. A non-woven product comprising a curedcomposition of claim
 1. 32. A latex extender comprising a curedcomposition of claim
 1. 33. A paint comprising a cured composition ofclaim
 1. 34. The composition of claim 7 wherein the dry weight ratio of(A) to (B) is about 5:1 to 1:1.
 35. The composition of claim 34, furthercomprising a fluoacid.
 36. A metal substrate coated with a curedcomposition of claim
 35. 37. The metal substrate of claim 36, whereinthe fluoacid is selected from at least one of fluotitanic acid andfluozirconic acid.
 38. The metal substrate of claim 37, wherein thecomposition has a pH from about 1.5 to about 5.0.
 39. A cellulosicproduct comprising a cured composition of claim
 34. 40. A latex extendercomprising a cured composition of claim
 34. 41. A non-woven productcomprising a cured composition of claim
 34. 42. A method of preparing acoated substrate which comprises: (1) coating a substrate with a coatingcomposition comprising: (A) at least one water-soluble componentcomprising at least one functional group that undergoes a crosslinkingreaction; and (B) at least one film-forming polymer; and (2) curing thecoating composition on the substrate.
 43. The method of claim 42 whereinsaid coating composition is dried in place on surface of said substrate.44. The method of claim 42 further comprises rinsing said coatingcomposition from said coated substrate.
 45. The method of claim 44wherein component (A) is selected from at least one of acrylamide-basedcrosslinkable polymers, polyamidoamine-epihalohydrin resins, polyamines,and polyimines.
 46. The method of claim 45 wherein component (A)comprises acrylamide-based crosslinkable polymers.
 47. The method ofclaim 45 wherein component (A) comprises cationic functionalizedpolyacrylamides.
 48. The method of claim 45 wherein the functional groupof component (A) is selected from at least one of epoxy, azetidinium,aldehyde, carboxyl group, acrylate and derivatives thereof, acrylamideand derivatives thereof, and quaternary amine.
 49. The method of claim48 wherein the functional group of component (A) is selected from atleast one of epoxy and azetidinium.
 50. The method of claim 45 whereinthe film-forming polymer is selected from at least one polymer derivedfrom monomers of alkyl halides of from 2-12 C atoms, alkene halides offrom 2-12 C atoms, alkyl acrylamides of from 2-12 C atoms, alkeneacrylamides of from 2-12 C atoms, alkyl acrylates of from 2-12 C atoms,and alkene acrylates of from 2-12 C atoms.
 51. The method of claim 50wherein the film-forming polymer is selected from at least one polymerderived from at least one monomer selected from at least one of styrene,dimethylstyrene, vinyltoluene, chloroprene, butadiene, ethylene,acrylamide, acrylonitrile, acrolein, methylacrylate, ethylacrylate,acrylic acid, methacrylic acid, methyl methacrylate, n-butyl acrylate,vinylidene chloride, vinyl ester, vinyl chloride, vinyl acetate,acrylated urethane, hydroxyethyl acrylate,dimethylaminoethyleneacrylate, and vinyl acetate.
 52. The method ofclaim 45 wherein the film-forming polymer is a latex selected from atleast one polymer derived from at least one monomer comprising repeatingunits derived from an alkyl halide having at least one double bond andan alkene, wherein the alkyl halide has from 2 to 12 C atoms, andwherein the alkene has from 2 to 12 C atoms.
 53. The method of claim 52wherein the alkyl halide comprises a vinyl halide and the alkenecomprises an olefin.
 54. The method of claim 52, wherein the alkylhalide comprises a vinyl halide and the alkene comprises ethylene. 55.The method of claim 50 wherein the dry weight ratio of (A) to (B) isabout 5:1 to 1:1.
 56. The method of claim 55 wherein the dry weightratio of (A) to (B) is about 1.69:1.
 57. The method of claim 50 furthercomprising a fluoacid.
 58. The method of claim 55 further comprising afluoacid.
 59. A metal substrate prepared by the method of claim
 57. 60.The metal substrate of claim 59, wherein the fluoacid is selected fromat least one of fluotitanic acid and fluozirconic acid.
 61. The metalsubstrate of claim 60 wherein the composition has a pH from about 1.5 toabout 5.0.
 62. A metal substrate prepared by the method of claim
 58. 63.The metal substrate of claim 62, wherein the fluoacid is selected fromat least one of fluotitanic acid and fluozirconic acid.
 64. The metalsubstrate of claim 63, wherein the composition has a pH from about 1.5to about 5.0.
 65. The method of claim 47 wherein the film-formingpolymer is selected from at least one polymer derived from monomers ofalkyl halides of from 2-12 C atoms, alkene halides of from 2-12 C atoms,alkyl acrylamides of from 2-12 C atoms, alkene acrylamides of from 2-12C atoms, alkyl acrylates of from 2-12 C atoms, and alkene acrylates offrom 2-12 C atoms.
 66. The method of claim 65 wherein the dry weightratio of (A) to (B) is about 2:1 to 1:1.
 67. The method of claim 66,further comprising a fluoacid selected from at least one of fluotitanicacid and fluozirconic acid.
 68. A metal substrate coated with a curedcomposition of claim
 67. 69. A method of preparing cellulosic productswhich comprises: substantially simultaneously or sequentially adding toa system comprising cellulosic fibers, wherein the system is selectedfrom at least one of aqueous system, felt, web, and combinations thereof(A) at least one water-soluble component comprising at least onefunctional group that undergoes a crosslinking reaction; and (B) atleast one film-forming polymer.
 70. The method of claim 69 whereincomponent (A) is selected from at least one of acrylamide-basedcrosslinkable polymers, polyamidoamine-epihalohydrin resins, polyamines,and polyimines.
 71. The method of claim 70 wherein component (A)comprises acrylamide-based crosslinkable polymers.
 72. The method ofclaim 71 wherein component (A) comprises cationic functionalizedpolyacrylamides.
 73. The method of claim 70 wherein the functional groupof component (A) is selected from at least one of epoxy, azetidinium,aldehyde, carboxyl group, acrylate and derivatives thereof, acrylamideand derivatives thereof, and quaternary amine.
 74. The method of claim73 wherein the functional group of component (A) is selected from atleast one of epoxy and azetidinium.
 75. The method of claim 70 whereinthe film-forming polymer is selected from at least one polymer derivedfrom at least one monomer derived from monomers of alkyl halides of from2-12 C atoms, alkene halides of from 2-12 C atoms, alkyl acrylamides offrom 2-12 C atoms, alkene acrylamides of from 2-12 C atoms, alkylacrylates of from 2-12 C atoms, and alkene acrylates of from 2-12 Catoms.
 76. The method of claim 75 wherein the film-forming polymer isselected from at least one polymer derived from at least one monomerselected from at least one of styrene, dimethylstyrene, vinyltoluene,chloroprene, butadiene, ethylene, acrylamide, acrylonitrile, acrolein,methylacrylate, ethylacrylate, acrylic acid, methacrylic acid, methylmethacrylate, n-butyl acrylate, vinylidene chloride, vinyl ester, vinylchloride, vinyl acetate, acrylated urethane, hydroxyethyl acrylate,dimethylaminoethyleneacrylate, and vinyl acetate.
 77. The method ofclaim 70 wherein the film-forming polymer is a latex selected from atleast one polymer derived from at least one monomer comprising repeatingunits derived from an alkyl halide having at least one double bond andan alkene, wherein the alkyl halide has from 2 to 12 C atoms, andwherein the alkene has from 2 to 12 C atoms.
 78. The method of claim 77wherein the alkyl halide comprises a vinyl halide and the alkenecomprises an olefin.
 79. The method of claim 77, wherein the alkylhalide comprises a vinyl halide and the alkene comprises ethylene. 80.The method of claim 75 wherein the dry weight ratio of (A) to (B) isabout 5:1 to 1:1.
 81. The method of claim 80 wherein the dry weightratio of (A) to (B) is about 1.69:1.
 82. The method of claim 72 whereinthe film-forming polymer is selected from at least one polymer derivedfrom monomers of alkyl halides of from 2-12 C atoms, alkene halides offrom 2-12 C atoms, alkyl acrylamides of from 2-12 C atoms, alkeneacrylamides of from 2-12 C atoms, alkyl acrylates of from 2-12 C atoms,and alkene acrylates of from 2-12 C atoms.
 83. The method of claim 82wherein the dry weight ratio of (A) to (B) is about 5:1 to 1:1.
 84. Themethod of claim 83 wherein the dry weight ratio of (A) to (B) is about2:1 to 1:1.
 85. A cellulosic product prepared by the method of claim 84.86. A ceiling tile prepared by the method of claim
 84. 87. A non-wovenproduct prepared by the method of claim
 84. 88. A method for forming asubstantially chromium-free, dried in place conversion coating on ametal surface comprising applying to a metal surface: (1) an aqueouscomposition comprising (A) at least one water-soluble componentcomprising at least one functional group that undergoes a crosslinkingreaction; and (B) at least one film-forming polymer; and (2) fluoacid,wherein the amount of the composition in (1) is from about 0.1 to about90% by weight, and wherein the amount of fluoacid is from about 0.2 toabout 20% by weight.
 89. The method of claim 88, wherein the fluoacid isselected from at least one of fluotitanic acid and fluozirconic acid.90. The method of claim 89, wherein the composition has a pH from about1.5 to about 5.0.
 91. The method of claim 90 wherein component (A) isselected from at least one of acrylamide-based crosslinkable polymers,polyamidoamine-epihalohydrin resins, polyamines, and polyimines.
 92. Themethod of claim 91 wherein component (A) comprises acrylamide-basedcrosslinkable polymers.
 93. The method of claim 92 wherein thefunctional group of component (A) is selected from at least one ofepoxy, azetidinium, aldehyde, carboxyl group, acrylate and derivativesthereof, acrylamide and derivatives thereof, and quaternary amine. 94.The method of claim 93 wherein the functional group of component (A) isselected from at least one of epoxy and azetidinium.
 95. The method ofclaim 91 wherein the film-forming polymer is selected from at least onepolymer derived from monomers of alkyl halides of from 2-12 C atoms,alkene halides of from 2-12 C atoms, alkyl acrylamides of from 2-12 Catoms, alkene acrylamides of from 2-12 C atoms, alkyl acrylates of from2-12 C atoms, and alkene acrylates of from 2-12 C atoms.
 96. The methodof claim 95 wherein the film-forming polymer is selected from at leastone polymer derived from at least one monomer selected from at least oneof styrene, dimethylstyrene, vinyltoluene, chloroprene, butadiene,ethylene, acrylamide, acrylonitrile, acrolein, methylacrylate,ethylacrylate, acrylic acid, methacrylic acid, methyl methacrylate,n-butyl acrylate, vinylidene chloride, vinyl ester, vinyl chloride,vinyl acetate, acrylated urethane, hydroxyethyl acrylate,dimethylaminoethyleneacrylate, and vinyl acetate.
 97. The method ofclaim 89 wherein the film-forming polymer is a latex selected from atleast one polymer derived from at least one monomer comprising repeatingunits derived from an alkyl halide having at least one double bond andan alkene, wherein the alkyl halide has from 2 to 12 C atoms, andwherein the alkene has from 2 to 12 C atoms.
 98. The method of claim 95wherein the dry weight ratio of (A) to (B) is about 5:1 to 1:1.
 99. Themethod of claim 98 wherein the dry weight ratio of (A) to (B) is about1.69:1.
 100. A metal substrate prepared by the method of claim
 88. 101.A metal substrate prepared by the method of claim
 89. 102. A metalsubstrate prepared by the method of claim
 95. 103. A metal substrateprepared by the method of claim
 98. 104. A coating compositioncomprising: (A) at least one polyamidoamine-epihalohydrin resin; and (B)at least one material in an amount sufficient to impart a cuttabilityvalue of less than about 15 to a substrate coated with the cured coatingcomposition.
 105. The coating composition of claim 104, wherein thecuttability value is less than about
 10. 106. The coating composition ofclaim 105, wherein the cuttability value is less than about
 2. 107. Thecoating composition of claim 106, wherein the cuttability value is lessthan about
 1. 108. A coating composition comprising: (A) at least onepolyamidoamine-epihalohydrin resin; and (B) at least one materialselected from flexibilizing materials, crosslink inhibiters andcombinations thereof in an amount sufficient to impart a cuttabilityvalue of less than about 15 to a substrate coated with the coatingcomposition.
 109. The coating composition of claim 108, wherein thecuttability value is less than about
 10. 110. The coating composition ofclaim 109, wherein the cuttability value is less than about
 2. 111. Thecoating composition of claim 110, wherein the cuttability value is lessthan about
 1. 112. The composition of claim 104, wherein (B) is selectedfrom copolymers derived from monomers including at least one of alkylhalides, alkenes, methyl methacrylate, butyl acrylate, styrenevinylidene chloride, acrylic acid, methacrylic acid, and vinylacrylic-based materials.
 113. A coating composition comprising: (A) atleast one polyamidoamine-epihalohydrin resin; and (B) at least onepolymer comprising repeating units derived from an alkyl halide havingat least one double bond and an alkene.
 114. The coating composition ofclaim 113, wherein the alkyl halide comprises a vinyl halide.
 115. Thecoating composition of claim 113, wherein the alkyl halide comprises avinyl halide and the alkene comprises an olefin.
 116. The coatingcomposition of claim 113, wherein the alkyl halide comprises a vinylhalide and the alkene comprises ethylene.
 117. The coating compositionof claim 115, wherein the vinyl halide comprises vinyl chloride. 118.The coating composition of claim 116, wherein the alkyl halide comprisesa vinyl chloride and the alkene comprises ethylene.
 119. The coatingcomposition of claim 113, wherein component (A) comprises an aqueoussolution of component (A) present in an amount in a range of from about5% to about 95% by weight based on the total weight of all components ofthe composition, and component (B) comprises an aqueous emulsion ofcomponent (B) present in an amount in a range of from about 5% to about95% by weight based on the total weight of all components of thecomposition.
 120. The coating composition of claim 119, whereincomponent (A) comprises an aqueous solution of component (A) present inan amount in a range of from about 50% to about 85% by weight based onthe total weight of all components of the composition, and component (B)comprises an aqueous emulsion of component (B) present in an amount in arange of from about 8% to about 50% by weight based on the total weightof all components of the composition.
 121. The coating composition ofclaim 120, wherein component (A) comprises an aqueous solution ofcomponent (A) present in an amount of about 75% by weight based on thetotal weight of all components of the composition, and component (B)comprises an aqueous emulsion of component (B) present in an amount ofabout 11% by weight based on the total weight of all components of thecomposition.
 122. The coating composition of claim 113, furthercomprising a surfactant.
 123. The coating composition of claim 122,wherein the surfactant comprises an octylphenoxypolyethoxyethanolnonionic surfactant.
 124. The coating composition of claim 122, whereinthe surfactant is present in an amount of up to about 5%, by weight.125. The coating composition of claim 124, wherein the surfactant ispresent in an amount of up to about 1% by weight.
 126. The coatingcomposition of claim 125, wherein the surfactant is present in an amountof about 0.05-0.25% by weight.
 127. A substrate, coated with the coatingcomposition of claim
 104. 128. A coated building unit comprising asubstrate and the coating of claim
 104. 129. The coated building unit ofclaim 128, wherein the substrate comprises a ceiling tile.
 130. Thecoated building unit of claim 128, wherein the substrate comprises awall board.
 131. The coated building unit of claim 128, which exhibits aHess Rake Test Value of at least about 8, and a cuttablity value of lessthan about
 15. 132. The coated building unit of claim 131, whichexhibits a Hess Rake Test Value of at least about 10, and a cuttablityvalue of less than about
 10. 133. The coated building unit of claim 132,which exhibits a Hess Rake Test Value of at least about 12, and acuttablity value of less than about
 2. 134. The coated building unit ofclaim 133, which exhibits a Hess Rake Test Value of at least about 14,and a cuttablity value of less than about
 1. 135. A building unit coatedwith a composition comprising: (A) at least onepolyamidoamine-epihalohydrin resin; and (B) at least one polymercomprising repeating units derived from an alkyl halide having at leastone double bond and an alkene.
 136. The coated building unit of claim135, wherein the substrate comprises a ceiling tile.
 137. The coatedbuilding unit of claim 135, wherein the substrate comprises a wallboard.
 138. The coated building unit of claim 135, which exhibits a HessRake Test Value range of at least about 8, and a cuttability value ofless than about
 15. 139. The coated building unit of claim 138, whichexhibits a Hess Rake Test Value of at least about 10, and a cuttabilityvalue of less than about
 10. 140. The coated building unit of claim 139,which exhibits a Hess Rake Test Value of at least about 12, and acuttability value of less than about
 2. 141. The coated building unit ofclaim 140, which exhibits a Hess Rake Test Value of at least about 14,and a cuttability value of less than about
 1. 142. A coating compositioncomprising: (A) at least one polyamidoamine-epihalohydrin resin; and (B)at least one material in an amount sufficient to impart sufficientflexibility, such that when the coating is applied to a substrate andcured, the cured coating exhibits substantially no delamination from thesubstrate or cracking, when the substrate is bent substantially 180°subsequent to curing.
 143. The composition of claim 142, wherein thethickness of the coating after curing is in the range of about 5-10 milswhen cured.
 144. The composition of claim 142, wherein the sufficientflexibility, is such that when the coating is applied to a substrate andcured, the cured coating exhibits substantially no delamination orcracking, when the substrate is bent substantially 360°.
 145. Asubstrate, coated with the coating composition of claim
 142. 146. Acoated building unit comprising a substrate and the coating of claim143.
 147. The coated building unit of claim 146, wherein the substratecomprises a ceiling tile.
 148. The coated building unit of claim 146,wherein the substrate comprises a wall board.
 149. The coatingcomposition of claim 142, wherein (B) is selected from copolymersderived from monomers including at least one of alkyl halides, alkenes,methyl methacrylate, butyl acrylate, styrene vinylidene chloride,acrylic acid, methacrylic acid, and vinyl acrylic-based materials. 150.A method of producing a coated substrate comprising (1) coating asubstrate with a coating composition comprising: (A) at least onepolyamidoamine-epihalohydrin resin; and (B) at least one material in anamount sufficient to impart a cuttability value of less than about 15 tothe coated substrate upon curing the coating composition; and (2) curingthe coating composition on the substrate.
 151. The method of claim 150,wherein the cuttability value is less than about
 10. 152. The method ofclaim 151, wherein the cuttability value is less than about
 2. 153. Themethod of claim 152, wherein the cuttability value is less than about 1.154. The method of claim 153, wherein the substrate comprises a buildingunit.
 155. The method of claim 154, wherein the building unit comprisesa ceiling tile.
 156. The method of claim 154, wherein the building unitcomprises a wall board.
 157. The method of claim 150, wherein thematerial of (2) comprises at least one polymer comprising repeatingunits derived from an alkyl halide having at least one double bond andan alkene.
 158. The coating composition of claim 157, wherein the alkylhalide comprises a vinyl halide.
 159. The method of claim 158, whereinthe alkyl halide comprises a vinyl halide and the alkene comprises anolefin.
 160. The method of claim 158, wherein the alkyl halide comprisesa vinyl halide and the alkene comprises ethylene.
 161. The method ofclaim 160, wherein the vinyl halide comprises vinyl chloride.
 162. Themethod of claim 150, wherein (B) is selected from copolymers derivedfrom monomers including at least one of alkyl halides, alkenes, methylmethacrylate, butyl acrylate, styrene vinylidene chloride, acrylic acid,methacrylic acid, and vinyl acrylic-based materials.
 163. The method ofclaim 150, wherein component (A) comprises an aqueous solution ofcomponent (A) present in an amount in a range of from about 5% to about95% by weight based on the total weight of all components of thecomposition, and component (B) comprises an aqueous emulsion ofcomponent (B) present in an amount in a range of from about 5% to about95% by weight based on the total weight of all components of thecomposition.
 164. The method of claim 163, wherein component (A)comprises an aqueous solution of component (A) present in an amount in arange of from about 50% to about 85% by weight based on the total weightof all components of the composition, and component (B) comprises anaqueous emulsion of component (B) present in an amount in a range offrom about 8% to about 50% by weight based on the total weight of allcomponents of the composition.
 165. The method of claim 164, whereincomponent (A) comprises an aqueous solution of component (A) present inan amount of about 75% by weight based on the total weight of allcomponents of the composition, and component (B) comprises an aqueousemulsion of component (B) present in an amount of 11% by weight based onthe total weight of all components of the composition.
 166. Thecomposition of claim 104, wherein the weight ratio of (A):(B) is fromabout 0.05 to about
 19. 167. The composition of claim 104, wherein theweight ratio of (A):(B) is from about 4 to about
 12. 168. Thecomposition of claim 104, wherein the weight ratio of (A):(B) is fromabout 6 to about
 8. 169. The composition of claim 104, wherein theweight ratio of (A):(B) is from about 6.5 to about 7.0
 170. Thecomposition of claim 104, wherein the weight ratio of (A):(B) is about6.75.
 171. The method of claim 150, wherein the weight ratio of (A):(B)is from about 0.05 to about
 19. 172. The method of claim 150, whereinthe weight ratio of (A):(B) is from about 4 to about
 12. 173. The methodof claim 150, wherein the weight ratio of (A):(B) is from about 6 toabout
 8. 174. The method of claim 150, wherein the weight ratio of(A):(B) is from about 6.5 to about 7.0
 175. The method of claim 150,wherein the weight ratio of (A):(B) is about 6.75.